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Modeling of large systems and charge transfer reaction mechanisms utilizing electronic structure theory

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Modeling of large systems and charge transfer reaction mechanisms utilizing electronic structure theory
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Wolfbrandt, Carly Taylor ( author )
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University of Colorado Denver
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University of Colorado Denver
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Department of Chemistry, CU Denver
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Chemistry

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Charge exchange ( lcsh )
Molecular structure -- Mathematical models ( lcsh )
Charge exchange ( fast )
Molecular structure -- Mathematical models ( fast )
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bibliography ( marcgt )
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by Carly Taylor Wolfbrandt.

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Full Text
MODELING OF LARGE SYSTEMS AND CHARGE TRANSFER REACTION
MECHANISMS UTILIZING ELECTRONIC STRUCTURE THEORY
by
CARLY TAYLOR WOLFBRANDT B.S., University of Colorado Denver, 2013
A thesis submitted to the Faculty of the Graduate School of the University of Colorado in partial fulfillment of the requirements for the degree of Master of Science Chemistry Program
2017


This thesis for the Master of Science degree by Carly Taylor Wolfbrandt
has been approved for the
Chemistry Program
by
Haobin Wang Hai Lin Scott Reed
May 13, 2017
11


Wolfbrandt, Carly Taylor (M.S., Chemistry Program)
Modeling of Large Systems and Charge Transfer Reaction Mechanisms Utilizing Electronic Structure Theory
Thesis directed by Professor Haobin Wang
ABSTRACT
Electronic structure theory calculations were used to investigate two systems: modeling of stable structures of RNA oligomers and photoinduced reaction mechanisms for photoremovable protecting groups (PPGs). For the first system, density functional theory (DFT) was performed on strands and duplexes of RNA oligomers of varying length, from 3 to 6 nitrogenous bases, referred to as trimers [CGA] and 6mers [CGAGCU], T-0-2-thiophenylmethyl functionalization induced changes in the torsional angle 8 (C5'-C4'-C3-03) and phosphate-phosphate distances, indicating a compacted structure consistent with experimental results. This structural information, along with experimental data, will be useful in designing stable compounds. The second study concerns the mechanism for deprotection of carbonyl groups from PPGs. The primary step of this reaction was found to be an ultrafast charge transfer reaction, which is followed by a dissociation reaction due to the transfer of energy to the reaction coordinate from the radiationless decay. This mechanism provides insight into the viability of deprotection with multiple wavelengths, allowing for increased temporal and spatial control in photoinduced chemical reactions.
The form and content of this abstract are approved. I recommend its publication.
Approved: Haobin Wang
m


ACKNOWLEDGMENTS
I would like to thank my advisor, Dr. Haobin Wang, for his patience, encouragement, and expert advice throughout my time in his group. Dr. Wangs door was always open when I had a question about my research or writing. This work would not have been possible without his tireless efforts, both in prioritizing my needs as a group member and as a student in the department.
A special thanks to Dr. Hai Lin for making himself available to answer odd questions, provide insight, and making me feel as though I was an honorary member of his research group. The Lin lab supported me greatly, as colleagues and as friends, and were always willing to lend a hand. I couldnt have asked for a better group to share the basement.
I would also like to thank the groups of Drs. Scott Reed and Marino Resendiz for their brilliance in the laboratory. Their experimental insights provide crucial context for this computational work.
Furthermore, I must express my gratitude to my parents and partner for their support and motivation. Thank you for being understanding and providing me continuous encouragement, especially when things were particularly stressful. This absolutely would not be possible without you. Thank you.
Finally, this project would have been impossible without support from the National Science Foundation (NSF) and the National Energy Research Scientific Computing Center (NERSC).
IV


TABLE OF CONTENTS
I. INTRODUCTION
Computational Chemistry......................................................1
Theory, Functionals, and Computational Methods...............................1
Hartree-Fock Theory.......................................................1
Density Functional Theory.................................................3
II. MOLECULAR MODELING OF OLIGONUCLEOTIDES OF RNA...............................6
Synthetically Modified Oligonucleotides of RNA ..............................6
Introduction..............................................................6
Investigated Systems......................................................7
Computational Methods.....................................................9
Model Systems and Nature of Stability in Modified RNA.......................10
Trimer Model System Results..............................................10
6mer Model System Results................................................12
Oligonucleotides of Interest for Further Study...........................15
Conclusions.................................................................15
III. ELECTRON TRANSFER IN PHOTOCHEMICAL REACTIONS...............................17
Theoretical Background......................................................17
Introduction.............................................................17
Kinetic Model of Electron Transfer.......................................17
Transition State Theory..................................................18
Marcus Theory of Electron Transfer.......................................20
Generalized Mulliken-Hush Method.........................................22
v


IV. ELECTRON TRANSFER MECHANISM..............................................24
Photoremovable Protecting Groups.........................................24
Introduction..........................................................24
Investigated Systems..................................................25
Proposed Deprotection Mechanism..........................................26
Mechanism Overview....................................................26
Franck-Condon Excitation: AEi.........................................28
Radiationless Decay: AE2..............................................30
Transition State Barrier: AE3.........................................31
Generalized Mulliken-Hush Coupling Results............................32
Summary...............................................................33
PPGs of Interest for Further Study.......................................33
Conclusions...............................................................35
IV. CONCLUSION...............................................................36
Conclusions...............................................................36
REFERENCES...................................................................38
APPENDIX
A. Additional Figures and Data for Chapter II...........................43
B. Additional Figures and Data for Chapter IV...........................45
C. Cartesian Coordinates (A) and Absolute Energies for the Optimized Structures.47
vi


CHAPTER I
INTRODUCTION Computational Chemistry
Computational chemistry is a fast-evolving discipline, the primary concern of which is the modeling of chemical systems. The advent of massively parallel computing systems has allowed for computer simulations of larger and more complicated systems without having to rely solely on classic mechanical descriptions. Furthermore, the relative inexpensive nature of computation makes it a valuable tool when used in conjunction with experimental chemistry. For instance, predictions in chemical behavior can be made with computational methods and used to support experimental findings. In this way, computational and experimental chemistry support and strengthen each other.
Theory, Functionals, and Computational Methods Hartree-Fock Theory
The task of electronic structure theory is to solve the time-independent, non-relativistic Schrodinger equation for electrons
Rw = ev (l.i)
which has the form of an eigenvalue equation for the total energy, E, and the ^-electron wave function V,1 The electronic Hamiltonian specifies the kinetic, T, and potential, V, energies for each electron
H = f + V (1.2)
The solution of the Schrodinger equation is based on the Born-Oppenheimer approximation, which assumes the nuclei are stationary from the perspective of the electrons. This allows separable treatment of the nuclear and electronic contributions. The nuclear repulsion term
1


is treated as an external potential and is added total energy Hamiltonian. The resulting electronic Hamiltonian is given by
H T + Vne + Vee
electrons
2meZji
vf-
4TtEn
^electrons
y nuclei %'a_ _f___
A rlA 4TtE0'
1electrons
Zj
electrons J_ r,
i]
(1.3)
where the first two terms constitute the one-electron Hamiltonian and the last term is the two-electron interaction which is responsible for the electron correlation effect. The core of various approximate numerical methods is how to handle electron correlations efficiently.
To satisfy the Pauli exclusion principle, the set of single electron basis functions in the form of spin orbital functions, Xi, are combined in the form of a Slater determinant to ensure that the wave function remains anti-symmetric. In the simplest, one-determinant form, the wave function is expressed as
W = -£=
Vnl
xi xl- Xn
xl Xi'" xl
zi1 x2- n An
(1.4)
where each row or column represents an individual electron/ This ensures that when two electrons exchange, the wave function changes sign and thus remains anti-symmetric. Neglecting electronic correlations, the iterative solution leads to the so-called Hartree-Fock (HF) approximation.
An obvious drawback to the HF method is that the many-electron wave function is forced into the form of a Slater determinant which only accounts for electron-electron interactions in an average way. The difference between the true energy and the HF energy, termed correlation energy, is completely ignored. There are various post self-consistent field (SCF) methods that can include (approximately) the correlation energy, e.g., perturbation
2


methods, configuration interaction approaches, coupled cluster theory, and multiconfiguration methods. These approaches appear to be too expensive when the size of the molecular system becomes very large. A compromise is to use Density Functional Theory (DFT) which has built in corrections, though they are very often semi-empirical.
Density Functional Theory
In 1964, Hohenberg and Kohn proposed two formal theorems for obtaining the ground-state energy based upon the electronic density, p{ r)4 Their work was motivated by the Thomas-Fermi model, but utilized a more solid theoretical foundation. 4 The Hamiltonian is expressed as a function of density
H = T (p) + Vee(p) + Vext (1.5)
In the case of a nondegenerate ground state, the electronic density in the ground state is given by
P(r) = (1-6)
In 1965, Kohn and Sham built upon the aforementioned work and proposed a set of self-consistent equations which include approximations for electronic exchange and correlation.5 These equations, known as the Kohn-Sham equations, invoke non-interaction electronic interaction for a fictitious system.5 What makes modern DFT calculations feasible is owed largely to the Kohn-Sham approximation, which has a computational scaling similar to HF but is capable of achieving higher accuracy.
DFT was well known in solid-state physics in the 1970s, but was not considered accurate enough by chemists. The main contributor who led DFT to its practical regime is Axel Becke; he introduced accurate approximations for the exchange-correlation functional that are beyond simple physical arguments.6 An example is the hybrid functional which
3


mixes pure DFT with HF contributions. This works surprisingly well in practice (despite having no obvious theoretical foundation) as demonstrated by Beckes 88 exchange functional and the correlation functional of Lee, Yang and Parr (B3LYP).6'7 Today, the usage of B3LYP is nearly ubiquitous, despite there being hundreds of proposed functionals, each with their own pros and cons.
The DFT theorem can also be applied to obtain excited state properties of a system, which is the main idea behind time-dependent density functional theory (TDDFT). This method was formally proposed in 1984 by Runge and Gross. The time-dependent Schrodinger equation is given by
RW(r,t) = ihjW(r,t') (1.7)
where the Hamiltonian has the form
H(t)=f(p)+Vee(p) + ^ext (t) (1.8)
Runge and Goss work focused on defining how electrons move in a time-dependent external potential. Their theorem was employed in the formulation of TDDFT by utilizing the change in external potential over time to generate the density.9 In our work, a linear response approximation of the TDDFT was used to obtain the excited state properties of the system.
To solve the Kohn-Sham SCF equation, program packages such as Gaussian 09 use Gaussian basis sets to approximate the atomic orbitals.10 In principle, the larger the basis set, the more accurate the expected results. In this work we calibrate the calculations with different basis set functions. The systematic naming scheme proposed by Pople was used; for example, in the basis set 3-21G, each inner shell is represented by a contracted basis function from three primitive Gaussian functions, and the outer valence orbitals are described by two sets of contracted basis functions with two and one primitive Gaussians, respectively.11 The
4


6-31G basis is a reasonably large basis set in this naming scheme. Furthermore, the addition of an asterisk (*) at the end of the basis set add polarization functions (V-orbital for main group elements).10 Diffuse functions may also be added (+) which are particularly useful in cases where electronic transfer is observed.
In cases where van der Waals interactions (dispersion forces) become important, empirical corrections are included via the D3 model of Grimme. For the linear-response TDDFT calculations, there is a fundamental defect for long-range charge-transfer excited
states. This is partially compensated by either a long-range corrected (LC) functional, or a
12
similar scheme such as the Coulomb-attenuating method (CAM-B3LYP).
For calculations in strong polar solvents, such as water, an implicit solvation model is used to emulate the reaction environment. The Polarizable Continuum Model (PCM) emulates a solvent by treating the solution as a dielectric continuum. Embedding the solute in a cavity surrounded by continuous media, the electron density is used to model the electrostatic potential of the solute and the solvent reaction field is made self-consistent with this potential.1014-16
5


CHAPTER II
MOLECULAR MODELING OF OLIGONUCLEOTIDES OF RNA Synthetically Modified Oligonucleotides of RNA
Introduction
Ribonucleic acid (RNA) is a biological macromolecule with essential uses in the human body. RNA in its natural form is primarily composed of the four nucleobases -adenine (A), guanine (G), cytosine (C) and uracil (U), as shown in Figure 2.1. Adenine and guanine are heterocyclic bases belonging to the purine group, while cytosine and uracil belong to the pyrimidine group.
O
A 0
1 p N 1
H H
Cytosine Uracil
Figure 2.1 Nucleobases of RNA
When these nitrogenous bases combine with ribose and a phosphate group they form a nucleotide; nucleotides are monomer units, as shown in Figure 2.2, which polymerize to form oligonucleotides (ONs) of RNA.19
6


Figure 2.2 Nucleotide of RNA with the nitrogenous base guanine
The most common naturally occurring RNA ONs are formed with the bases from Figure 2.1. Synthetically modified RNA can be formed by altering the nucleobase or adding functional groups to the ribose ring. One example is uridine modified at the C5-position (numbered positions shown in Figure 2.10) with the small functional group thiophene; this modified nucleobase was found to be accommodated by T7 RNA polymerase, albeit in low yields. Another common place to modify is the ribose ring at the C2-0-position, as shown in Figures 2.2 and 2.3.19 Examples of modifications at this position with small functional groups have been discussed by Nakamura et al. and indicate that the size of thiophene will
21 24
allow for compatibility with biological processes.
Investigated Systems
Thiophene functionalization carried out at the ribose ring results in varying numbers
25
of modifications per strand, from single to fully modified oligonucleotides. Figure 2.3 indicates the position of the modifications.
7


Figure 2.3 Overview of 2-0-2-thiophenylmethyl functionalization
Duplexes were formed from the modified and unmodified strands. Figure 2.4 shows the formation of a modified duplex, where each strand has four modifications and each duplex has eight. Unmodified (canonical) duplexes were also studied.
8


Figure 2.4 Formation of a duplex from two strands functionalized with four T -0-2-thiophenylmethyl groups
These complexes were compared with their canonical analogues using strands and
duplexes in varying lengths, from 3 to 6 nitrogenous bases, referred to as trimers and
"6mers". The sequences can be found in Figures 2.5 and 2.6
1 5-CGA 3 5-CGA
2 GCU-5' 4 GCU-5'
Figure 2.5 Sequence of trimer oligonucleotides 1:2 (canonical) and 3:4 (modified) where the underlined nucleotides represent 2'-0-2-thiophenylmethyl modified positions.
5 5- C G A GC U 7 5-CGAGCU
6 GCUCGA-5' 8 GCUCGA-5'
Figure 2.6 Sequence of 6mer oligonucleotides 5:6 (canonical) and 7:8 (modified) where the underlined nucleotides represent 2'-G-2-thiophenyl methyl modified positions.
Computational Methods
To shed light on the effect that a 2-methylthiophenyl group has on single and double strands of RNA, we performed electronic structure calculations using DFT on modified complexes of RNA containing 2-G-2-thiophenyl methyl groups. Calculations were performed using the quantum chemistry program Gaussian 09.10 The B3LYP hybrid
9


functional with both 3-21G* and 6-31G* basis sets were used in geometry optimizations, along with the PCM implicit solvent approach and Grimmes empirical dispersion correction.6,13-14 Gas phase calculations were unable to model the RNA duplexes, therefore it was necessary to use PCM to emulate the reaction environment. Calculations with dispersion corrections more closely modeled the helical backbone and matched experimental data showing tightening of the helix.
Model Systems and Nature of Stability in Modified RNA Trimer Model System Results
Due to the size and complexity of the systems, initial geometry optimizations were performed on canonical and modified trimers. The sequences of these molecules can be found in Figure 2.5. Optimizations using single strands supported that the duplex is the thermodynamically favored conformation.
To better understand the stabilities, free energy calculations were performed on 1:2 and 3:4 at the 3-21G* level. Frequency calculations are expensive, therefore it was ideal to perform these calculations on a small trimer model system. Vant Hoff plots can be seen in Figures 2.7 and 2.8.
10


-AG/RT
Figure 2.7 Vant Hoff plot for modified trimer (300-400 K at 10 K increments) where AG = -15.8753 kcal mol'1 AH = -39.1042 kcal mol'1 and AS = -77.4296 cal mol'1 K'1
11


Figure 2.8 Vant Hoff plot for canonical trimer (300-400 K at 10 K increments)
where AG = -20.4236 kcal mol'1 AH = -44.8528 kcal mol'1 and AS = -81.4308 cal mol'1 K'1
As can be seen from these Vant Hoff plots, due to the negative AG values, we expect these two reactions to be spontaneous at low temperatures. The formation of the canonical trimer has slightly more free energy, the enthalpy is more negative and the magnitude of the negative entropy change is larger. Therefore, we expect this reaction to be very slightly more favorable. However, due to the inherent error in these calculations, it should be noted that this evidence is inconclusive.
6mer Model System Results
Duplexes 5:6 and 7:8 were optimized at both the 3-21G* and 6-31G* levels; their sequences can be found in Figure 2.6 and images in Figure 2.9. Optimizations using single strands supported that the duplex is the thermodynamically favored conformation.
12


Figure 2.9 Side by side comparison of the optimized structures of 5:6 (left) and 7:8 (right).
Since a free energy calculation was not feasible for a model system of this size, with 5:6 and 7:8 having over 450 atoms each, other methods to assess the stability had to be employed. A common method is the study of torsional angles and phosphate-phosphate bond distances, with shorter bonds being indicative of a more compact and stable structure.
Quantitative analysis was performed by measuring the torsion angles % (glydosidic dihedral angle between sugar and nucleobase) and 8 (backbone dihedral angle along the ribose ring). Figures 2.2 and 2.10 define these values.
13


group
X
5
pyrimidine 04-Ci-Ni-C2 Cs-C^-Cs-Os
purine O4-C1-N9-C4 C5-C4-C3-03
sr^'N


N'
1
vs
3 n
8
a
A
V
Figure 2.10 Torsion angles % and 8 and phosphate-phosphate distance, a with numbering ring for pyrimidine (left) and purine (right).2 "27
The covariance matrix for these angles can be seen in Figure 2.11. The first thing to notice about Figure 2.11 is that the angles obtained from our calculations are in the region corresponding to A-form geometries, -140 > % < -170 0 and 65 > 8 < 100.25 Secondly, the modified 6mer can be found clustered in a region of lower 8 values, which indicate stability since a smaller 8 implies a tighter backbone angle, and therefore a tighter helix.
8()
too
95
90
85
80
75
70
65
-170




-165







-160
-155
X()
-150
-145
-140
Canonical Modified
Figure 2.11 A plot displaying the (x, 8) angle covariance matrix
14


Table 2.1 Phosphate-phosphate bond distances from optimized 3-21G* 6mer Phosphate-Phosphate Bond Distances A
Canonical Modified
5.9 0.4
5.5 0.3
The phosphate-phosphate distances, a from Figure 2.10, can be seen in Table 2.1 where shorter bond distances indicate stability of the 6mer.
Oligonucleotides of Interest for Further Study
To shed further light on the nature of stability induced by these modifications, calculations were performed on duplexes with varying degrees of modification. Modified duplexes 9:6, 10:6, 11:6, 7:6 are being optimized at the 6-31G* level.
9 5-CGAGCU 10 5-CGAGCU 11 5-CGAGCU
Figure 2.12 Sequence of oligonucleotides with varying degrees of substitution where the underlined nucleotides represent 2-G-2-thiophenyl methyl modified positions.
Once the optimizations are complete, these strands and duplexes can be analyzed the same way as above; measuring the torsion angles % (glydosidic dihedral angle between sugar and nucleobase) and 8 (backbone dihedral angle along the ribose ring) and comparing them to assess stability induced or diminished by staggered functionalization.
Conclusions
Synthetically modified RNA can produce functional nucleotides with many applications ranging from nanomaterials to gene therapy. Thiophene was chosen as it allows the ability to expand the possible functionalizations of interest. Thiophene is also attractive due to the small size, which helps prevent structural disruptions to the backbone, and properties which allow for chemical reactions without disrupting the native biochemical processes of RNA. A stabilizing effect was found when complementary nucleobases of
15


ONs of RNA were modified at the C2-O-position. The covariance matrix for the dihedral angles obtained from our calculations are in the region corresponding to A-form geometries. Moreover, the modified 6mer can be found clustered in a region of lower 8 values, indicating increased stability. These results are in congruence with experimental findings, and further research is needed to investigate the destabilizing effect when modifications are
25
intercalated.
Using computational methods, we can model very large oligonucleotide systems using an electronic theory approach. Traditionally, these types of molecules have been modeled using mixed quantum and classical mechanics, due to restrictions in computing power and time. Recent advancements in computational power have enabled us to forgo classic mechanical approximations in favor of a full DFT investigation. The largest system investigated in this study (over 450 atoms) was optimized using both smaller and larger basis sets (3-21G* and 6-31G*) and support experimental findings. The error margin is still large for many quantitative results, but that does not diminish the importance of the qualitative findings.
16


CHAPTER III
ELECTRON TRANSFER IN PHOTOCHEMICAL REACTIONS Theoretical Background
Introduction
The following chapter introduces the kinetic model of electron transfer, Eyrings transition state theory, Marcuss theory of electron transfer, and the Generalized Mulliken-Hush method. These sections set the theoretical groundwork for the proposed electron transfer mechanism given in Chapter IV.
Kinetic Model of Electron Transfer
Engel and Reid have outlined a kinetic model of electron transfer reactions, where electron transfer reactions are defined as outer-sphere redox reactions where an exchange of charge between a donor molecule (D) and an acceptor (A) molecule occurs. These reactions are ubiquitous in chemistry and biology; the most prevalent is the photosynthetic reaction of CO2 and H20 to form sugars and 02.
6C2(g) + 6H2G) C6Hi206(s) + 602(g) (3.1)
In Reaction (3.1), the acceptor C02 is reduced while the donor H20 is oxidized. A generalized electron transfer reaction can be written as
D + A ^ D+ + A- (3.2)
A reaction mechanism can also be written to describe electron transfer in a bimolecular reaction. The first step of the reversible reaction is the formation of a donor-acceptor complex
kd
D+A^DA (3.3)
17


Next, electron transfer occurs between the donor and acceptor in the complex, leaving each species with a charge, or back-electron transfer occurs in the complex, reforming the donor-acceptor complex
DA ^ D+A-
kbet
(3.4)
The final step is the separation of the complex into isolated oxidized donor and reduced acceptor molecules
Transition State Theory
In the 1930s, Edward Eyring developed a theoretical model for reaction rates and barriers, known as Transition State Theory (TST).32 Theoretically, reactions are thought to pass over an energy barrier, with reactants on one side and products on the other. When the molecule is at the height of the barrier, it is said to be a transition state, as shown in Figure
(3.5)
3.1.
18


Gibbs
Free
Energy
Figure 3.1 Adiabatic plot of Gibbs free energy versus the reaction coordinate for an exothermic reaction where AG* is the Gibbs energy of activation
We can use this theory to form the following equations:
/Ci
DA ^ DA* (3.6)
fc-i
DA* -> D+ + A- (3.7)
where the transition state, DA*, is equivalent to the D+A_ complex from Reaction (3.4).31 As shown in Figure 3.1, the experimentally determined rate constant will have a dependence on the Gibbs energy of activation.
Transition state theory has several known limitations, namely the assumption that
32
there exists an equilibrium between the donor-acceptor complex and the transition state.
This implies that each transition state has time to equilibrate and reach a Boltzmann distribution. Furthermore, it relies on a classical mechanical description of the nuclei and neglects tunneling effects.
19


Marcus Theory of Electron Transfer
Rudolph Marcus earned a Nobel prize for his work on redefining the relationship in
33 39
Reaction (3.7) using a diabatic representation of electron transfer. A graph illustrating the connection between Gibbs energy and the rate constant can be seen in Figure 3.2.
Figure 3.2 Diabatic plot of Gibbs free energy versus the reaction coordinate for the normal Marcus regime where X is the reorganization energy
Marcus made important determinations regarding the chemical factors that affect
AG* in particular the solute/solvent effects of electron transfer. He proposed that the solute and solvent with relax following electron transfer; the solute will relax to a new equilibrium geometry following electron transfer as the bonds reorder and nuclei relax, and the solvent will respond to the change in charge distribution following electron transfer. He related these relaxations, referred to as the reorganization energy, X, to the Gibbs energy of activation in the following manner
AG* =
(AG+A)2
4A
(3.8)
20


Marcus theory proposes other regimes, where different values for AG are shown by different overlap in the parabolic potential energy surfaces, as shown in Figures 3.2 and 3.3. As Equation (3.8) shows, there is a minimum when AG = A. It is predicted that the rate will increase with AG until a maximum rate occurs when AG = A then the rate will decrease. The inverted regime can be seen in Figure 3.3.
Figure 3.3 Diabatic plot of Gibbs free energy versus the reaction coordinate for the inverted Marcus regime
This inverted behavior indicates that extra energy is needed to reach the crossing point. Per the Franck-Condon principle, this motion of electron transfer can be expressed as a vertical transition due to the speed at which excitation occurs; the nuclear geometry is estimated to remain constant during this transition. During this fast electron transfer process, the nuclei have no time to change positions and the electron transfer can occur at the reactant
21


and product intersection. Theoretically, this location has the highest probability due to the wave function overlap between the reactant and products.
Generalized Mulliken-Hush Method
Robert Cave and Marshall Newton utilized Marcus theory in their development of the Generalized Mulliken-Hush (GMH) theory.40'41 GMH predicts that, in electron transfer reactions, charges are localized on donor and acceptor centers. This allows for the construction of diabatic states from adiabatic states.
Figure 3.4 Diabatic (left) and adiabatic (right) plots where HDa is the matrix coupling element
These diabatic states can be constructed from the Hamiltonian and dipole operator eigenstate matrices given by
H =
H
\Ei 1
[o E2\
Mi Ml2
-Ml2 M2-
(3.9)
_ r Mi M121 I-Ml2 M2 j
(3.10)
where ^ is the ground state dipole, ji2 is the excited state dipole and ji12 is the transition dipole. A unitary transformation of fi yields
22


(3.11)
H
liR 0 0 [iP
which can be used to transform the eigenstate Hamiltonian to the charge-localized states
H =
Ed Hda Hda EA .
(3.12)
where
Hda
J(Ul~U2)2+4Ul2
(3.13)
A graphical representation of the above values is given in Figure 3.5.
Potential
Energy
Figure 3.5 Potential energy diagram for constructing diabatic states from an adiabatic representation by the GMH method
The weak coupling limit is given by
kDA = Y\HDA\2-
(A+AGy
4 XkgT
(3.14)
yjAnXksT
where the Marcus electron transfer rate, kDA, is defined by the electronic coupling, HDA, the reorganization energy, 1, and the standard Gibbs free energy, AG.
23


CHAPTER IV
ELECTRON TRANSFER REACTION MECHANISM Photoremovable Protecting Groups
Introduction
Photoremovable protecting groups (PPGs) provide a means of exciting one group of molecules with light while leaving another inactive, resulting in a controlled release of various chemicals. Neurotransmitters, pheromones, fragrances, acids, bases, and oxidants can all be released by PPGs.43 There have been many developments in applications of PPGs with particular emphasis on the release of organic molecules.42'44
The importance of cyclic acetals as carbonyl PPGs lies in their stability and lack of reactivity.45'46 Two representations of one protecting group molecule can be seen in Figure 4.1.
Figure 4.1 Two representations of a model PPG where the substitutions on the left molecule are Ri = H and R2 = -(CH2)2Ph.
Cyclic acetals are formed by the reaction of a carbonyl with two alcohol equivalents and the removal of water, which is an important feature since acetal formation is reversible in acidic environments. Once a carbonyl is converted to an acetal, it is unreactive in neutral or basic environments and can be exposed to strongly nucleophilic compounds without concern.
24


Investigated Systems
Photoexcitation reactions of the PPGs for carbonyl compounds, shown in Figure 4.2, were chosen based on multi-disciplinary relevance as well as the availability of experimental
47
and simulation data suggesting a plausible mechanistic pathway.
OMe
1. = H R2 = H
2. R1 = H R2 = -(CH2)2Ph
Figure 4.2 Model PPGs 1-6
OMe
3. Rt = H R2 = H
4. R1 = H R2 = -(CH2)2Ph
5. Rt = H R2 = H
6. R1 = H R2 = -(CH2)2Ph
It was suggested that 1 and 2 should be the most likely to dissociate, due to the
excited-state meta effect. PPGs driven by the meta effect are said to dissociate more readily due to the donation of electron density in C-l facilitating the benzylic C-0 dissociation.47'50
Furthermore, it has been shown by Zimmerman and co-workers that meta-directing groups
stabilize cations, lending heterolysis of the C-0 bond to be energetically favored over homolysis.48'50 The expected zwitterionic transition state and products in this reaction can be
seen in Figure 4.3.
25


OMe
OMe


O
MeO'
CH2+
+
MeO
OH
7
8
Figure 4.3 Proposed transition state, 1*, (R1/R2 = H) and products 7 and 8, where 8 is the protected carbonyl of interest
The lack of possibility for free radicals, along with the presence of structural features which help delocalize charge, enhance the attractiveness of the system for computational
background for the proposed deprotection mechanism; in particular, the kinetic model of electron transfer, Eyrings transition state theory, Marcuss electron transfer theory, and the Generalized Mulliken-Hush method are discussed in detail.
Mechanism Overview
Deprotection is proposed to occur as follows (representations can be found in Figures 4.4 and 4.5): (blue, 1) the molecule experiences Franck-Condon excitation upon irradiation, (red, 2) reorganization energy is small and there is not a large change in the excited state geometry, so the molecule quickly undergoes radiationless decay (purple, 3) the molecule maintains sufficient energy to overcome the transition state barrier (blue, 4) the molecule dissociates. A representation of the molecules at each point can be seen in Figure 4.4.
study.43
In order to fully understand a theoretically proposed mechanism, one must first
understand the theory behind the calculations. Chapter III discusses the theoretical
Proposed Deprotection Mechanism
26


Figure 4.4 Franck-Condon energy level diagram shown with molecular representations of the reaction.
As shown in Figure 4.5, photoexcitation at point A leads to a vertical transition to point B. Relaxation occurs rapidly from point B to point C, where internal conversion allows for radiationless decay to point D. The molecule still possesses sufficient energy at point D to overcome the boundary and dissociate.
27


Excited State
Ground State
Figure 4.5 Franck-Condon energy level diagram with naming conventions for excitation, deexcitation and the energy at the transition state.
The next sections will go through the calculated transitions step by step. Franck-Condon Excitation: AEi
Before absorption occurred, each molecule occupied the lowest vibrational state of its lowest electronic state after optimization using DFT at the 6-31G* level and the B3LYP hybrid functional.51 Linear approximation TDDFT calculations at the 6-31G* level indicated the most likely excited states for each molecule. Excitation energies can be found in Table 4.1.
28


Table 4.1 Excitation energies, AEi, for molecules 1-6 using TDDFT at the 6-31G* level and B3LYP hybrid functional
molecule AEi (eV)
1 6.0867
2 6.2727
3 6.6734
4 6.6484
5 6.8559
6 6.6757
Per the Franck-Condon principle, this motion is expressed as a vertical transition due to the speed at which excitation occurs; the nuclear geometry is estimated to remain constant during this transition.51 This vertical excitation passes through many vibrational levels in the upper electronic state, therefore there are many accessible vibrational states for the molecules to now occupy. Theoretically, the molecules have the highest probability of occupying the upper vibrational state that has the most overlap with the ground state wave function.51 A fundamental assumption of the Franck-Condon principle is the separation of the electronic and vibrational wave functions, known as the Born-Oppenheimer approximation.
There was no indication that dissociation occurred after excitation. TDDFT single point energy calculations at the 6-31G* level showed no dissociation, and optimizations allowed for vibrational relaxation to the lowest vibrational state of the highest excited electronic state also did not dissociate. Since the molecule has so much excess energy at this point, a remaining option for the molecules is to undergo internal conversion and transition to the ground electronic state.
29


Radiationless Decay: AE2
The molecules transitioned to the ground electronic state through internal conversion, also described as radiationless decay since there is no emission of a photon in this process. De-excitation energies can be found in Table 4.2.
Table 4.2 De-excitation energies, AE2, for molecules 1, 3-6 using TDDFT at the 6-31G* level and B3LYP hybrid functional
molecule AE2 (eV)
1 3.8114
3 4.3044
4 3.6428
5 4.7201
6 5.3076
The remaining energy is then transferred to the vibrational modes of the molecule. This remaining energy, which is the difference in the excitation and de-excitation energies (AEi -AE2), can be seen in Table 4.3.
Table 4.3 Energy remaining (AEi -AE2) for molecules 1, 3- 6 after radiationless decay for each molecule
molecule Remaining Energy (eV)
1 2.2753
3 2.3690
4 3.0056
5 2.1358
6 1.3681
30


Transition State Barrier: AE3
Transition states were found using Gaussian 09 by requesting a minimization to a transition state rather than a local minimum. The transition state is defined as a first-order saddle point on the potential energy surface where, like minima, the forces are all zero; unlike minima, at a saddle point one of the second derivatives is negative. The transition state was found by manually building a guess structure and following the eigenvector corresponding with this negative eigenvalue to the saddle point.10 If a true transition state is reached, there will be only one imaginary frequency which arises from the reaction coordinate. Although this is a costly calculation, calculating the Hessian at each step ensures that the correct eigenvector is followed to the true transition state structure. The energy of the molecule at the transition state can then be compared to the energy at the optimized ground state to obtain the energy height of the barrier.
Table 4.4 Transition state energy barrier, AE3. for each molecule using DFT at the 6-31G* level and B3LYP hybrid functional
molecule ae3
1 1.8336
2 1.5456
3 1.8128
4 1.6573
5 1.8479
6 1.6944
As can be seen by comparing Figures 4.3 and 4.4, the energy remaining after radiationless decay exceeds the energy required to overcome the transition state barrier. If the
31


excess energy is released as heat, the molecules would never show any indications of dissociation. These molecules were found to dissociate readily upon irradiation per experimental data, so the excess energy must be transferred to the reaction coordinate to overcome the transition state barrier.
Generalized Mulliken-Hush Coupling Results
The Generalized Mulliken-Hush (GMH) method, a useful scheme discussed in detail in Chapter III, was used to calculate diabatic electron transfer coupling. Since TDDFT with commonly used functionals is usually not correct for charge-transfer problems, we performed calculations with LRC density functionals, which yields better coupling results for charge-transfer states. The calculations were performed at the 6-31G* level in Q-Chem 4.4 developer version and results are shown in Table 4.5.54
Table 4.5 Coupling results for charge-transfer states using GMH method at the transition state
molecule coupling (eV)
1 1.1823
2 0.2378
3 1.3625
5 1.3687
4 1.3932
6 1.3607
Radiationless decay can be described as a transition between two different diabatic states, where excess energy is released through the vibrational modes. When coupling is large (greater than 1 eV), the reaction can be assume to proceed at the sub-picosecond timescale. On average, fluorescence takes nanoseconds which cannot compete in these types
32


of ultrafast reactions. Since the coupling was calculated to be strong, the competition between radiationless and radiational decay can be ignored.
Summary
Molecules 1-6 are proposed to dissociate in the following manner an ultrafast charge transfer reaction where the primary driving force for dissociation is the transfer of energy to the reaction coordinate following radiationless decay. There are no indications that these molecules will fluoresce, since the coupling is so large. The molecules possess sufficient energy following radiationless decay in order to overcome the transition state barrier. There are no indications that molecules 1 and 2 will dissociate more readily than molecules 3-6. However, it is worth noting that converged higher excited states of molecule 2 were unable to be reached. Furthermore, its coupling constant is lower than the others by an order of magnitude. A more in depth study of this molecule might prove interesting; there is a possibility for a competing mechanism for dissociation, such as steric hindrance from the larger R group.
PPGs of Interest for Further Study
Photochemical reactions involving PPGs have been used extensively in organic synthesis, however, the selectivity of specific protecting groups to different wavelength combinations has not been widely studied.4347 Our research, in collaboration with Dr. Scott Reeds experimental group at the University of Colorado Denver, indicated that multiple-wavelength photo-deprotection is possible.
Two molecules, shown in Figure 4.6, were studied computationally with different R groups to assess whether multiple-wavelength deprotection was possible. The R groups chosen were anthracene and anisole, due to differences in their lmax.
33


9. = anthracene, R, = anisole, R3 = H, R4 = H 11. R, = anthracene, R, = anisole, R3 = H,
10. R( = anthracene, R, = H, R3 = anisole, R4 = H 12. R( = anthracene, R, = H, R3 = anisole,
Figure 4.6 Four multiple-wavelength PPGs with varying substitution sites
While initial studies are inconclusive as to the viability of deprotection with multiple wavelengths, there is indication that the Ri and R2 positions do not act independently. As shown in Table 4.7, TDDFT studies performed at the 6-31G* level indicate that the Amaris nearly the same independent of substitution site.
Table 4.6 2maTfor molecules 9-12 shown in Figure 4.5 with varying substitutions
molecule wavelength (nm)
9 241.52
10 237.92
11 240.75
12 236.92
Using information about PPGs 1-6, we have proposed a mechanism for the dual deprotection of molecule 12 in Scheme 4.1,43'47
34


Scheme 4.1 Proposed dual-wavelength deprotection mechanism of 10 in acidic conditions
Conclusions
Electronic structure theory calculations were conducted to shed light on the mechanism of dissociation in protecting group reactions. The reaction was found to be an ultrafast charge transfer reaction where the primary driving force for dissociation is the transfer of energy to the reaction coordinate following radiationless decay. There are no indications that molecules 1-6 will fluoresce, since the coupling is so large. The molecules must possess sufficient energy following radiationless decay in order to overcome the transition state barrier. There are no indications that molecules 1 and 2 will dissociate more readily than molecules 3-6. However, it is worth noting that converged higher excited states of molecule 2 were unable to be reached. Furthermore, its coupling constant is lower than the others by a full order of magnitude. A more in depth study of this molecule might prove interesting; there is a possibility for a competing mechanism for dissociation, such as steric hindrance from the larger R group. Further research is needed to establish whether or not dual wavelength deprotection is possible.
35


CHAPTER V
CONCLUSION
Conclusions
Synthetically modified RNA can produce functional nucleotides with many applications ranging from nanomaterials to gene therapy. Thiophene was chosen as it allows the ability to expand the possible functionalizations of interest. Thiophene is also attractive due to the small size, which helps prevent structural disruptions to the backbone, and properties which allow for chemical reactions without disrupting the native biochemical processes of RNA. A stabilizing effect was found when complementary nucleobases of ONs of RNA were modified at the C2-O-position. The covariance matrix for the dihedral angles obtained from our calculations are in the region corresponding to A-form geometries. Moreover, the modified 6mer can be found clustered in a region of lower 8 values, indicating increased stability. These results are in congruence with experimental findings, and further research is needed to investigate the destabilizing effect when modifications are
25
intercalated.
Photo-induced chemical reactions are of fundamental importance in chemistry, biochemistry and materials science. A comprehensive understanding of such reaction mechanisms is crucial for designing novel electronic and optical materials, next generation solar cells, and alternative synthetic methods. Deprotection of the carbonyl from PPGs 1-6 was found to be an ultrafast charge transfer reaction where the primary driving force for dissociation is the transfer of energy to the reaction coordinate following radiationless decay. There are no indications that molecules 1 and 2 will dissociate more readily than molecules 3-6. A more in depth study of molecule 2 might prove interesting for a possible competing
36


mechanism. Further research is needed to establish whether or not dual wavelength deprotection is possible.
From organic synthesis to quantum calculations, the ability to predict chemical changes is constantly evolving as technology advances. As computers become more and more advanced, they allow for quantum chemical calculations on increasingly larger systems. The large systems of interest herein (some greater than 450 atoms) take advantage of the recent strides in computational science. Computational studies are especially effective when used in conjunction with synthetic chemistry, either concurrently with experimental analysis or predictively. The latter case is particularly useful, as reliable computational studies can facilitate synthetic endeavors.
37


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42


APPENDIX A
ADDITIONAL FIGURES AND DATA FOR CHAPTER II

Figure A.l Side by side comparison of the optimized structures canonical (left) and modified (right) dimers. Dashed lines within the helix represent hydrogen bonds between the strands.
50 45 40 35




r AG o25 < 1 20 15 10




0 0.0( 334
324 0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0( 1/T
Figure A.2 Vant Hoff plot for canonical dimer (300-400 K at 5 K increments) where AG = -27.0113 kcal mol'1, AH = -44.1013 kcal mol'1 and AS = -56.9666 cal mol'1 K'1
43


-AG/RT
Figure A.3 Vant Hoff plot for modified dimer (300-400 K at 5 K increments) where AG = -24.2594 kcal mol'1 AH = -39.3520 kcal mol'1 and AS = -50.3086 cal mol'1 K'1
44


APPENDIX B
ADDITIONAL FIGURES AND DATA FOR CHAPTER IV Table B.l Coupling results for charge-transfer states using GMH method at the ground state
molecule excitation energy (eV) oscillator strength coupling (eV)
2 4.8723 0.067760 2.426818
1 4.8408 0.064740 2.393382
3 4.7949 0.067444 2.383986
5 5.1553 0.033592 2.179227
4 4.7709 0.064236 2.367367
6 5.1356 0.034174 2.112277
Table B.2 Coupling results for charge-transfer states using GMH method at the excited state
molecule excitation energy (eV) oscillator strength coupling (eV)
2 4.6379 0.066374 2.295142
1 3.9875 0.080361 1.734402
3 4.3947 0.076263 2.194795
5 4.7954 0.048902 2.071878
4 4.3813 0.073712 2.182455
6 4.7717 0.049159 2.010648
45


Table B.4 Transition state to excited state gap for each molecule using TDDFT at the 6-31G* level and B3LYP hybrid functional
molecule ae4
1 3.2085
2 1.9435
3 3.2447
5 3.4276
4 3.3028
6 3.4795
46


APPENDIX C
CARTESIAN COORDINATES (A) FOR THE OPTIMIZED STRUCTURES IN
CHAPTERS II and IV
CHAPTER II 1 0.592177000 0.929775000 -2.496422000
1 SCF E(RB3LYP) = -3854.60801632 au 1 0.962727000 3.259321000 -3.201189000
B3LYP/3-21G* opt EmpiricalDispersion=GD3 SCRF(PCM) 1 2.654033000 5.103446000 -3.312397000
nosymm scf=xqc 8 7.323678000 3.225082000 -5.559071000
1 1.965512000 6.578618000 -5.437784000 6 8.490975000 0.010105000 -3.829601000
8 2.755617000 6.195621000 -4.973736000 6 8.986705000 -0.372677000 -5.227928000
6 5.081890000 5.101738000 -2.228680000 6 8.899176000 0.964328000 -5.981506000
6 6.067536000 4.689484000 -3.324417000 6 9.312453000 1.977162000 -4.910406000
6 5.422535000 5.310548000 -4.580770000 6 8.729273000 3.355194000 -5.121282000
6 4.918127000 6.652370000 -4.038148000 8 8.804659000 1.420139000 -3.632927000
6 3.762186000 7.246665000 -4.813187000 1 8.956747000 -0.615875000 -3.067370000
8 4.478864000 6.359201000 -2.649361000 1 8.432386000 -1.199024000 -5.667856000
1 5.571123000 5.199769000 -1.261878000 8 10.414851000 -0.701483000 -5.124376000
1 6.205630000 3.613499000 -3.361526000 1 10.819929000 -0.158522000 -5.866842000
8 7.334065000 5.391089000 -3.109684000 1 7.906722000 1.179886000 -6.367974000
1 7.553420000 5.734174000 -4.028244000 1 10.404229000 2.031946000 -4.872136000
1 4.616740000 4.710401000 -4.998020000 1 9.283217000 3.870186000 -5.909225000
1 5.754699000 7.356350000 -4.014741000 1 8.746660000 3.924899000 -4.190009000
1 4.150732000 7.581819000 -5.783316000 8 9.898646000 1.015853000 -7.049870000
1 3.367578000 8.110498000 -4.265118000 7 4.761820000 -2.809615000 -1.853263000
8 6.443664000 5.589246000 -5.588859000 6 6.103999000 -3.109004000 -1.987609000
7 4.025519000 4.065361000 -2.122543000 7 6.549308000 -4.285189000 -1.505207000
6 4.386056000 2.870230000 -1.406833000 7 6.958406000 -2.270224000 -2.574164000
8 5.527100000 2.830317000 -0.893972000 6 6.379235000 -1.143750000 -3.041474000
7 3.461382000 1.869320000 -1.356767000 6 5.034619000 -0.757411000 -2.967823000
6 2.299136000 1.978426000 -2.012637000 6 4.119290000 -1.612684000 -2.293991000
7 1.495777000 0.889910000 -2.037663000 8 2.898433000 -1.487052000 -2.038241000
6 1.911767000 3.182788000 -2.691466000 7 4.866275000 0.482170000 -3.616596000
6 2.814605000 4.199362000 -2.736803000 6 6.072463000 0.836557000 -4.034932000
1 1.938079000 -0.025023000 -1.857118000 7 7.033761000 -0.125930000 -3.698552000
47


1
1
1
1
15
8
8
8
6
6
6
6
6
8
1
1
8
1
1
1
1
1
8
1
7
6
7
6
6
6
7
7
6
7
1
4.136141000 -3.462573000 -1.384035000 1 3.176923000 0.281064000 -4.692598000
5.947543000 -4.963550000 -1.055094000 1 1.776158000 -0.552175000 -4.159582000
7.534044000 -4.500550000 -1.608743000 1 6.991189000 -1.030149000 -7.534659000
6.341774000 1.728290000 -4.578168000 15 9.295793000 0.651795000 -8.571468000
6.748929000 4.327986000 -6.661223000 8 10.468029000 0.658740000 -9.498232000
7.866169000 4.814447000 -7.529092000 8 8.013691000 1.398748000 -8.767971000
5.441146000 3.787290000 -7.142621000 2 SCF E(RB3LYP) = -3802.42247134 au
8.829735000 -0.908876000 -8.263834000 B3LYP/3-21G* opt EmpiricalDispersion=GD3 SCRF(PCM)
7.002874000 -3.857640000 -7.054208000 nosymm scf=xqc
7.024503000 -4.337050000 -8.511591000 8 5.038238000 -7.812039000 2.966820000
8.109156000 -3.449730000 -9.164024000 6 6.366780000 -4.984918000 1.308008000
9.121732000 -3.270182000 -8.023687000 6 7.375854000 -4.870280000 2.459284000
9.853841000 -1.947801000 -8.069789000 6 7.325969000 -6.263626000 3.123592000
8.324021000 -3.302749000 -6.771404000 6 7.063721000 -7.199750000 1.932293000
6.774675000 -4.694789000 -6.392583000 6 6.211290000 -8.392899000 2.307326000
6.038673000 -4.256861000 -8.981195000 8 6.298490000 -6.395795000 0.945650000
7.554081000 -5.689374000 -8.505652000 1 6.713688000 -4.387556000 0.463646000
8.187385000 -5.675134000 -9.291180000 1 7.130502000 -4.044131000 3.134533000
7.732650000 -2.482952000 -9.494594000 8 8.692108000 -4.751340000 1.856698000
9.819711000 -4.111272000 -8.038225000 1 9.243957000 -5.379080000 2.422331000
10.562082000 -1.924776000 -8.902244000 1 6.529114000 -6.354580000 3.859958000
10.366971000 -1.786608000 -7.118763000 1 8.020949000 -7.501948000 1.500252000
8.798184000 -4.198121000 -10.217577000 1 6.749079000 -9.053956000 2.993641000
8.311668000 -4.060552000 -11.074579000 1 5.899931000 -8.928691000 1.407786000
2.454675000 -2.825345000 -4.862218000 8 8.648580000 -6.616747000 3.645636000
3.078978000 -3.995690000 -5.114928000 1 8.721298000 -6.280437000 4.579133000
4.275549000 -4.175247000 -5.719277000 7 3.199646000 -1.194051000 0.371966000
4.807338000 -3.012481000 -6.143181000 6 4.499082000 -1.391842000 -0.048730000
4.249159000 -1.734381000 -5.981549000 7 5.055040000 -0.473121000 -0.864314000
3.049392000 -1.658990000 -5.245007000 7 5.208632000 -2.456700000 0.323368000
2.501252000 -0.477797000 -4.869380000 6 4.537766000 -3.296891000 1.142934000
5.087411000 -0.763144000 -6.554984000 6 3.231333000 -3.182776000 1.624451000
6.124766000 -1.438910000 -7.038431000 6 2.429498000 -2.092268000 1.182778000
6.006952000 -2.817606000 -6.806186000 8 1.213027000 -1.860058000 1.350483000
2.570750000 -4.891942000 -4.779906000 7 2.918945000 -4.291296000 2.427215000
48


6
7
1
1
1
1
8
6
6
6
6
6
8
1
1
8
1
1
1
1
1
8
7
6
8
7
6
7
6
6
1
1
1
1
15
4.005669000 -5.050829000 2.432767000 8 4.543495000 -9.843645000 4.484817000
5.034207000 -4.481975000 1.649029000 8 2.993333000 -7.678385000 4.353041000
2.666609000 -0.407249000 0.006355000 1 -5.277087000 -4.455450000 -1.045654000
4.563907000 0.352935000 -1.181859000 8 -4.490439000 -5.024966000 -1.252430000
6.007812000 -0.623652000 -1.174050000 6 -1.840093000 -6.999544000 -2.902240000
4.115645000 -5.998404000 2.928560000 6 -1.251526000 -7.310930000 -1.515217000
-0.072826000 -7.431587000 1.820294000 6 -2.373735000 -6.809023000 -0.594327000
2.609446000 -7.777050000 -0.837842000 6 -3.629003000 -7.254804000 -1.343609000
3.522713000 -8.094484000 0.349544000 6 -4.858764000 -6.427569000 -1.040600000
2.541452000 -8.391232000 1.504969000 8 -3.281990000 -7.066421000 -2.782250000
1.369592000 -9.083013000 0.804791000 1 -1.467647000 -7.711570000 -3.637263000
0.017216000 -8.851828000 1.460989000 1 -0.313527000 -6.791709000 -1.350274000
1.353170000 -8.503676000 -0.569645000 8 -1.101005000 -8.749174000 -1.408511000
3.053638000 -8.101149000 -1.775523000 1 -0.103247000 -8.870363000 -1.289221000
4.240603000 -7.302939000 0.557683000 1 -2.339517000 -5.721916000 -0.534314000
4.204521000 -9.362452000 0.050565000 1 -3.803204000 -8.314827000 -1.140952000
4.063935000 -9.888929000 0.896689000 1 -5.137129000 -6.620979000 0.003278000
2.222590000 -7.507396000 2.051166000 1 -5.681161000 -6.735089000 -1.697525000
1.578377000 -10.152926000 0.730588000 8 -2.383744000 -7.386754000 0.734625000
-0.041074000 -9.475003000 2.359456000 7 -1.444559000 -5.629294000 -3.336124000
-0.777419000 -9.097057000 0.755968000 6 -0.100137000 -5.508515000 -3.702056000
3.137932000 -9.374121000 2.418500000 8 0.669106000 -6.486308000 -3.675014000
2.318402000 -6.344561000 -0.971162000 7 0.283343000 -4.229541000 -4.047853000
2.912306000 -5.629180000 -2.072342000 6 -0.508133000 -3.058403000 -4.017462000
3.752865000 -6.215125000 -2.781579000 8 0.014966000 -1.951408000 -4.260243000
2.516955000 -4.321924000 -2.251448000 6 -1.880694000 -3.307342000 -3.633160000
1.651206000 -3.744598000 -1.401935000 1 -2.549271000 -2.463599000 -3.569836000
1.282370000 -2.463941000 -1.620827000 6 -2.293539000 -4.550724000 -3.282716000
1.056701000 -4.450780000 -0.312335000 1 1.300107000 -4.098565000 -4.075203000
1.406552000 -5.746069000 -0.144280000 1 -3.275052000 -4.758679000 -2.870822000
1.500278000 -1.998926000 -2.496550000 15 -1.524864000 -6.623830000 1.931707000
0.705306000 -1.988689000 -0.933604000 8 -2.195593000 -6.954594000 3.227802000
0.336557000 -4.013141000 0.356084000 8 -1.221380000 -5.216295000 1.498450000
0.938481000 -6.350629000 0.619448000 1:2 SCF E(RB3LYP) = -7657.37918362
3.904447000 -8.707586000 3.755333000
49


B3LYP/3-21G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc 6 6 6.817939000 5.938130000 -7.053476000 -8.178489000 1.979605000 2.448995000
1 1.982674000 6.320589000 -5.443355000 8 6.154443000 -6.344471000 0.853388000
8 2.814324000 5.990842000 -5.010559000 1 7.028996000 -4.627290000 -0.019369000
6 5.234344000 5.108063000 -2.285451000 1 7.376957000 -3.790854000 2.578885000
6 6.225927000 4.735871000 -3.385540000 8 8.840739000 -5.042770000 1.654739000
6 5.546935000 5.307773000 -4.644236000 1 9.215671000 -5.592321000 2.412589000
6 4.956994000 6.622146000 -4.119071000 1 6.196324000 -5.759579000 3.609578000
6 3.745336000 7.116240000 -4.878046000 1 7.779920000 -7.450217000 1.643868000
8 4.562876000 6.323167000 -2.712322000 1 6.457935000 -8.755470000 3.216429000
1 5.737477000 5.252391000 -1.330309000 1 5.678138000 -8.816148000 1.602755000
1 6.419840000 3.672174000 -3.398467000 8 8.233972000 -6.405042000 3.801864000
8 7.454606000 5.504461000 -3.165383000 1 8.297644000 -5.830796000 4.612357000
1 7.683855000 5.846443000 -4.079314000 7 4.442941000 -0.366690000 0.150899000
1 4.776296000 4.651958000 -5.042763000 6 5.750460000 -0.768513000 -0.040158000
1 5.737306000 7.387025000 -4.117066000 7 6.615743000 0.148764000 -0.498864000
1 4.085977000 7.468163000 -5.858809000 7 6.169838000 -2.021149000 0.226168000
1 3.294534000 7.952590000 -4.332687000 6 5.198857000 -2.813533000 0.724165000
8 6.542828000 5.640745000 -5.670182000 6 3.870810000 -2.475156000 1.010220000
7 4.215882000 4.032362000 -2.110507000 6 3.418906000 -1.169751000 0.673882000
6 4.593144000 2.903069000 -1.355659000 8 2.242044000 -0.711392000 0.782843000
8 5.816042000 2.778862000 -1.044348000 7 3.198289000 -3.580709000 1.563316000
7 3.630044000 2.014018000 -0.999941000 6 4.094837000 -4.560824000 1.591926000
6 2.355346000 2.140547000 -1.448988000 7 5.328244000 -4.140729000 1.076065000
7 1.445579000 1.275074000 -1.000381000 1 4.143249000 0.583978000 -0.228485000
6 2.014008000 3.194799000 -2.360296000 1 6.338825000 1.128904000 -0.694679000
6 2.959124000 4.129093000 -2.645775000 1 7.556505000 -0.159448000 -0.719381000
1 1.719386000 0.525513000 -0.335407000 1 3.968443000 -5.554841000 1.982606000
1 0.489027000 1.316312000 -1.337227000 8 7.526490000 3.329611000 -5.568546000
1 1.023306000 3.258436000 -2.782867000 6 8.520234000 0.075531000 -3.835595000
1 2.786097000 4.953628000 -3.327447000 6 9.076604000 -0.302900000 -5.207363000
8 4.703066000 -7.593166000 3.027470000 6 9.001344000 1.037281000 -5.934911000
6 6.545556000 -4.933455000 0.907379000 6 9.450277000 2.029589000 -4.861646000
6 7.483915000 -4.772205000 2.109798000 6 8.921641000 3.427849000 -5.088521000
6 7.086676000 -5.958360000 3.015312000 8 8.901160000 1.468511000 -3.595611000
50


1
1
8
1
1
1
1
1
8
7
6
7
7
6
6
6
8
7
6
7
1
1
1
1
15
8
8
8
6
6
6
6
6
8
1
8.898701000 -0.573208000 -3.045176000 1 4.016132000 -7.387817000
8.528389000 -1.116785000 -5.671147000 8 4.098223000 -9.440174000
10.497720000 -0.650296000 -5.063085000 1 4.031833000 -9.972100000
10.951384000 -0.127863000 -5.785066000 1 1.938473000 -7.693910000
7.992351000 1.268624000 -6.258878000 1 1.603212000 -10.412683000
10.541192000 2.048117000 -4.800865000 1 -0.170909000 -9.985725000
9.515940000 3.919394000 -5.860491000 1 -0.835984000 -9.608701000
8.924126000 4.007223000 -4.164747000 8 3.020083000 -9.434141000
9.933195000 1.106496000 -7.060341000 7 2.027549000 -6.498100000
4.393579000 -2.636639000 -2.483383000 6 2.785798000 -5.629391000
5.688212000 -3.078420000 -2.653717000 8 3.785641000 -6.104158000
5.942152000 -4.370545000 -2.374085000 7 2.425389000 -4.326061000
6.682499000 -2.275653000 -3.076245000 6 1.355834000 -3.848732000
6.269445000 -1.028219000 -3.376629000 7 1.059474000 -2.560807000
4.968964000 -0.519647000 -3.296112000 6 0.598392000 -4.722047000
3.949112000 -1.340000000 -2.763339000 6 0.973475000 -6.021587000
2.749814000 -0.999674000 -2.534789000 1 1.664413000 -1.947891000
4.937355000 0.815276000 -3.727392000 1 0.364606000 -2.129440000
6.192126000 1.108696000 -4.040522000 1 -0.254456000 -4.396722000
7.049435000 0.017050000 -3.829530000 1 0.450902000 -6.719008000
3.637057000 -3.315886000 -2.155150000 15 3.695319000 -8.616806000
5.171154000 -5.057143000 -2.271976000 8 4.489814000 -9.642406000
6.880032000 -4.706707000 -2.567292000 8 2.643551000 -7.747976000
6.557917000 2.025695000 -4.465384000 8 8.733967000 -0.720474000
6.957693000 4.384221000 -6.694582000 6 7.237903000 -3.836132000
8.081389000 4.898602000 -7.543431000 6 7.187692000 -4.419229000
5.701720000 3.777198000 -7.241445000 6 8.070995000 -3.442599000
-0.386337000 -7.930871000 1.836759000 6 9.163362000 -3.080229000
2.416967000 -7.926801000 -0.748505000 6 9.804046000 -1.731097000
3.344728000 -8.216847000 0.425639000 8 8.488653000 -3.094807000
2.361196000 -8.567624000 1.562256000 1 7.181320000 -4.626439000
1.280097000 -9.375682000 0.830791000 1 6.161427000 -4.501074000
-0.116786000 -9.318177000 1.419044000 8 7.894180000 -5.690530000
1.233493000 -8.753462000 -0.530866000 1 8.436609000 -5.640301000
2.877722000 -8.152972000 -1.705157000 1 7.529727000 -2.558324000
51


1
1
1
8
1
7
6
7
6
6
6
7
7
6
7
1
1
1
1
15
8
8
1
8
6
6
6
6
6
8
1
1
8
1
1
9.928837000 -3.860222000 -7.966949000 1 -3.816210000 -8.722646000 -1.568236000
10.434854000 -1.748789000 -9.040091000 1 -5.383449000 -7.357817000 -0.330402000
10.400867000 -1.492926000 -7.267033000 1 -5.746590000 -7.173084000 -2.069771000
8.737825000 -4.156627000 -10.047419000 8 -2.587996000 -7.974614000 0.536733000
8.114183000 -4.190727000 -10.822717000 7 -1.499594000 -5.610052000 -3.156083000
2.472121000 -3.462042000 -4.896510000 6 -0.191943000 -5.319648000 -3.568127000
3.346277000 -4.494179000 -4.888835000 8 0.672036000 -6.220808000 -3.680499000
4.597067000 -4.479227000 -5.378132000 7 0.052713000 -3.997416000 -3.828745000
4.928861000 -3.278730000 -5.907515000 6 -0.813438000 -2.932125000 -3.613805000
4.117338000 -2.138050000 -5.964935000 8 -0.446484000 -1.750011000 -3.870933000
2.819375000 -2.245285000 -5.417005000 6 -2.106430000 -3.305697000 -3.094105000
1.929423000 -1.250135000 -5.369651000 1 -2.823713000 -2.529225000 -2.880911000
4.813239000 -1.078977000 -6.567769000 6 -2.411533000 -4.614150000 -2.903553000
6.009530000 -1.578981000 -6.878425000 1 1.029277000 -3.764871000 -4.216241000
6.124639000 -2.916921000 -6.493791000 1 -3.366137000 -4.939960000 -2.505525000
2.986899000 -5.399564000 -4.422742000 15 -1.915348000 -7.300569000 1.885469000
2.212913000 -0.317569000 -5.653368000 8 -2.664934000 -7.848820000 3.062909000
1.063058000 -1.374850000 -4.816001000 8 -1.728908000 -5.820962000 1.669015000
6.825793000 -1.065790000 -7.359882000 3 SCF E(RB3LYP) i= -4442.83103616 au
9.212610000 0.845174000 -8.536520000 B3LYP/3-21G* opt EmpiricalDispersion=GD3 scrf(pcm)
10.310093000 0.918500000 -9.553855000 nosymm scf=xqc
7.946679000 1.652168000 -8.612267000 1 8.671959000 19.165602000 -23.862360000
-5.618454000 -5.041473000 -1.064877000 8 9.217177000 19.262937000 -23.038195000
-4.751549000 -5.513044000 -1.179137000 6 10.151216000 18.797714000 -19.444666000
-1.828639000 -7.052740000 -2.967171000 6 11.406329000 19.606343000 -19.793143000
-1.329965000 -7.542339000 -1.602557000 6 11.039642000 20.247796000 -21.151253000
-2.538401000 -7.221451000 -0.709580000 6 9.534518000 20.500221000 -21.006553000
-3.708472000 -7.635458000 -1.602238000 6 8.784640000 20.467848000 -22.323316000
-5.018579000 -6.952173000 -1.281550000 8 9.028986000 19.411176000 -20.141738000
-3.272885000 -7.220012000 -2.971687000 1 9.998119000 18.786936000 -18.366997000
-1.360591000 -7.613773000 -3.774563000 1 12.306134000 18.993504000 -19.793960000
-0.438672000 -7.002798000 -1.316170000 8 11.522961000 20.705955000 -18.828048000
-1.112468000 -8.974947000 -1.656000000 1 11.646575000 21.508009000 -19.424217000
-0.141797000 -9.082939000 -1.388407000 1 11.257369000 19.614548000 -22.009052000
-2.581730000 -6.156516000 -0.498385000 1 9.387535000 21.464423000 -20.511181000
52


1
1
8
7
6
8
7
6
7
6
6
1
1
1
1
8
6
6
6
6
6
8
1
1
8
1
1
1
1
8
7
6
7
7
6
9.042437000 21.375634000 -22.882792000 6 13.002919000 15.568692000
7.707143000 20.458634000 -22.122814000 6 12.471844000 14.355442000
11.679068000 21.563315000 -21.277390000 8 11.482503000 14.153177000
10.273677000 17.394257000 -19.896082000 7 12.658689000 16.910603000
10.903617000 16.485247000 -18.981874000 6 13.450448000 17.635780000
11.359576000 16.950866000 -17.913971000 7 14.294225000 16.822986000
10.956956000 15.166166000 -19.348401000 1 12.900929000 12.335430000
10.493753000 14.777597000 -20.540740000 1 14.504965000 11.213010000
10.574180000 13.462079000 -20.852904000 1 15.531652000 12.155194000
9.924482000 15.687948000 -21.488416000 1 13.503545000 18.708958000
9.828928000 16.992166000 -21.124020000 15 13.120816000 21.573561000
11.039056000 12.834799000 -20.205982000 8 13.747664000 22.908454000
10.382309000 13.148119000 -21.798383000 8 12.875235000 20.943494000
9.680550000 15.358576000 -22.485316000 8 18.620801000 19.138113000
9.441862000 17.761402000 -21.783789000 6 18.372964000 15.655426000
13.907114000 20.417148000 -21.261245000 6 19.519144000 16.057564000
15.200693000 17.228487000 -20.090029000 6 20.062396000 17.355569000
16.580084000 17.698638000 -20.605928000 6 19.877590000 17.088910000
16.382902000 19.221507000 -20.715770000 6 19.641580000 18.337876000
15.405365000 19.583129000 -19.592761000 8 18.669683000 16.231371000
14.493734000 20.733319000 -19.954964000 1 18.298354000 14.567882000
14.603571000 18.347970000 -19.357646000 1 19.177883000 16.175170000
15.326183000 16.362312000 -19.437385000 8 20.563108000 15.059922000
16.848179000 17.229563000 -21.548328000 1 21.396985000 15.627090000
17.660891000 17.284795000 -19.720095000 1 19.514195000 18.248072000
15.902753000 19.452542000 -21.668403000 1 20.748997000 16.539452000
15.950663000 19.836108000 -18.682303000 1 20.565098000 18.918114000
15.079633000 21.653596000 -20.034190000 1 19.263945000 18.064102000
13.700650000 20.842599000 -19.210908000 8 21.505906000 17.456262000
17.589763000 20.011817000 -20.553580000 1 21.659037000 17.933820000
13.214729000 13.231807000 -22.493900000 7 13.806355000 14.351904000
14.222368000 13.275356000 -21.549242000 6 14.966857000 13.669659000
14.785878000 12.115411000 -21.158379000 7 16.140653000 14.111092000
14.647156000 14.423478000 -21.018082000 6 16.073234000 15.401320000
14.027512000 15.513468000 -21.517816000 6 14.946305000 16.236959000
53


6 13.752693000 15.641027000 -25.504134000 8 14.848206000 8.926691000 -16.460903000
7 12.550382000 16.269299000 -25.466402000 1 14.898158000 8.136130000 -15.835600000
7 15.254886000 17.509937000 -24.533886000 1 12.548152000 6.733933000 -17.554146000
6 16.527817000 17.435833000 -24.156613000 1 15.558145000 6.573082000 -17.779434000
7 17.072820000 16.166365000 -24.400710000 1 14.353259000 4.520404000 -18.330602000
1 14.951156000 12.646868000 -26.215123000 1 14.865939000 5.274835000 -19.889924000
1 12.456510000 16.975764000 -24.721396000 8 13.968685000 6.544798000 -15.954280000
1 11.757231000 15.627504000 -25.508299000 1 13.184987000 6.518411000 -15.341746000
1 17.117121000 18.210197000 -23.687661000 7 11.710540000 12.912314000 -20.743632000
15 18.227857000 20.598943000 -21.977928000 6 12.857380000 12.843666000 -19.974035000
8 19.473579000 21.336448000 -21.602669000 7 13.514064000 13.990082000 -19.704024000
8 17.123104000 21.149542000 -22.826887000 7 13.319126000 11.688826000 -19.500668000
6 17.704708000 17.898036000 -18.380457000 6 12.569952000 10.617873000 -19.848741000
1 18.031073000 18.936910000 -18.465652000 6 11.398926000 10.585338000 -20.608097000
1 16.710075000 17.860189000 -17.917279000 6 10.900634000 11.806962000 -21.138184000
6 19.294496000 17.324888000 -16.410171000 8 9.904833000 12.039284000 -21.864663000
6 18.680520000 17.066016000 -17.606374000 7 10.967071000 9.259519000 -20.762613000
16 19.122319000 15.499106000 -18.233630000 6 11.846846000 8.512331000 -20.106334000
6 20.138079000 15.192280000 -16.856016000 7 12.850281000 9.311617000 -19.514616000
6 20.134730000 16.242333000 -15.975340000 1 11.391791000 13.809724000 -21.105811000
1 19.157372000 18.243893000 -15.856579000 1 13.213519000 14.893226000 -20.048535000
1 20.692411000 14.269572000 -16.775807000 1 14.356600000 13.937007000 -19.143947000
1 20.706208000 16.258721000 -15.057696000 1 11.852117000 7.435297000 -20.056585000
4 SCF E(RB3LYP) = -4390.64826456 au 8 12.239741000 4.871892000 -25.111512000
B3LYP/3-21G* opt EmpiricalDispersion=GD3 scrf(pcm) 6 14.495381000 7.428304000 -23.583578000
nosymm scf=xqc 6 14.288409000 6.759862000 -22.218584000
8 12.833002000 5.527183000 -19.417543000 6 13.513934000 5.496884000 -22.634269000
6 14.015235000 8.939075000 -18.713907000 6 14.289484000 5.039404000 -23.869507000
6 13.669101000 8.618832000 -17.251884000 6 13.526301000 4.211101000 -24.891187000
6 13.533465000 7.080078000 -17.246461000 8 14.646308000 6.328669000 -24.526024000
6 14.587314000 6.649136000 -18.276037000 1 15.365051000 8.068605000 -23.655835000
6 14.233757000 5.373946000 -19.007579000 1 13.768771000 7.388533000 -21.500863000
8 14.618119000 7.742547000 -19.277739000 8 15.581198000 6.339108000 -21.672166000
1 14.704358000 9.784088000 -18.745913000 1 12.505129000 5.793950000 -22.915676000
1 12.771273000 9.149768000 -16.918935000 1 15.203722000 4.527701000 -23.561588000
54


1
1
8
7
6
8
7
6
7
6
6
1
1
1
15
8
8
1
8
6
6
6
6
6
8
1
1
8
1
1
1
1
1
8
7
13.379703000 3.196869000 -24.507111000 6 14.948500000 9.310778000 -26.414359000
14.111108000 4.189748000 -25.816028000 8 15.876505000 8.583610000 -26.017787000
13.437503000 4.451761000 -21.638067000 7 14.584249000 10.494928000 -25.801139000
13.303163000 8.242118000 -23.906628000 6 13.549069000 11.389043000 -26.184702000
13.265804000 9.568510000 -23.371388000 8 13.369435000 12.445182000 -25.558399000
14.316902000 10.010347000 -22.824625000 6 12.787692000 10.906718000 -27.316942000
12.108446000 10.261468000 -23.512202000 1 11.943042000 11.492601000 -27.643372000
11.042077000 9.722369000 -24.135906000 6 13.100914000 9.742741000 -27.930252000
9.889776000 10.419087000 -24.106082000 1 15.010439000 10.666038000 -24.886839000
11.112517000 8.446672000 -24.783798000 1 12.496512000 9.320453000 -28.723533000
12.252931000 7.733232000 -24.611937000 15 11.210976000 4.638150000 -26.386500000
9.051587000 10.023515000 -24.517935000 8 10.808608000 3.204278000 -26.493206000
10.300366000 7.988078000 -25.327139000 8 10.256975000 5.794134000 -26.293696000
12.344365000 6.720085000 -24.968238000 6 16.452381000 7.515205000 -21.413624000
12.155688000 4.569936000 -20.579921000 1 15.865896000 8.440378000 -21.440922000
11.899052000 3.192040000 -20.054331000 1 16.863753000 7.385993000 -20.411375000
11.088643000 5.438713000 -21.190676000 6 18.354755000 8.558259000 -22.844206000
10.179432000 8.483570000 -29.768216000 6 17.514225000 7.540147000 -22.475027000
11.004262000 8.152203000 -29.325385000 16 17.803897000 6.099201000 -23.410730000
14.541651000 7.701409000 -28.235419000 6 19.080528000 6.877702000 -24.294109000
14.082861000 6.508704000 -27.406042000 6 19.259336000 8.176958000 -23.893285000
12.643719000 6.316242000 -27.896283000 1 18.330239000 9.541476000 -22.394077000
12.795871000 6.563631000 -29.403127000 1 19.614054000 6.351511000 -25.071032000
11.533204000 7.025330000 -30.095714000 1 19.992082000 8.843656000 -24.326588000
13.822934000 7.642196000 -29.496347000 1 9.799885000 11.147174000 -23.379711000
15.618922000 7.701463000 -28.395573000 3:4 SCF E(RB3LYP) = -8833.66515618 au
14.207231000 6.659760000 -26.341204000 B3LYP/3-21G* opt EmpiricalDispersion=GD3 SCRF(PCM)
14.835314000 5.320037000 -27.838488000 nosymm scf=xqc
14.117736000 4.622418000 -27.912783000 1 8.327112000 20.906510000 -23.653007000
11.928285000 7.005137000 -27.454680000 8 8.856566000 20.562346000 -22.886526000
13.180363000 5.657062000 -29.877227000 6 9.695608000 18.674442000 -19.768271000
10.833307000 6.179823000 -30.106691000 6 11.082847000 19.305200000 -19.841918000
11.768142000 7.311125000 -31.127892000 6 10.890428000 20.388064000 -20.923380000
12.243665000 4.925144000 -27.675450000 6 9.483037000 20.903346000 -20.596611000
14.168405000 8.971327000 -27.527198000 6 8.751735000 21.509681000 -21.774096000
55


8
1
1
8
1
1
1
1
1
8
7
6
8
7
6
7
6
6
1
1
1
1
8
6
6
6
6
6
8
1
1
8
1
1
1
8.736975000 19.707039000 -20.123015000 1 16.301516000 5.202111000
9.495371000 18.270311000 -18.776712000 1 16.025674000 5.501601000
11.842906000 18.561227000 -20.042019000 8 15.676138000 7.195080000
11.332549000 20.010542000 -18.582110000 1 15.141601000 7.113548000
11.682081000 20.899732000 -18.893891000 7 11.008303000 12.838997000
10.959833000 20.008199000 -21.940687000 6 12.159857000 12.851669000
9.555648000 21.630163000 -19.783232000 7 12.479979000 14.006971000
9.238791000 22.463113000 -22.013853000 7 12.942691000 11.768609000
7.708628000 21.696548000 -21.493702000 6 12.458937000 10.673975000
11.825652000 21.491921000 -20.709474000 6 11.266895000 10.545783000
9.578988000 17.561448000 -20.754646000 6 10.497596000 11.713773000
10.125338000 16.309895000 -20.383102000 8 9.475452000 11.821184000
10.837929000 16.263966000 -19.340569000 7 11.110363000 9.223475000
9.830303000 15.231870000 -21.154767000 6 12.188997000 8.571097000
9.156853000 15.361416000 -22.322144000 7 13.049709000 9.426669000
8.852017000 14.256180000 -23.000767000 1 10.532192000 13.770104000
8.751968000 16.660954000 -22.781245000 1 11.893626000 14.860443000
8.949642000 17.724653000 -21.960155000 1 13.381689000 14.046895000
9.129886000 13.321037000 -22.631352000 1 12.393239000 7.510117000
8.375201000 14.320294000 -23.893544000 8 13.831352000 19.972776000
8.265366000 16.781703000 -23.737343000 6 15.442515000 16.696806000
8.666431000 18.736935000 -22.228262000 6 16.740502000 17.297187000
14.331572000 4.966727000 -19.559477000 6 16.366587000 18.785103000
14.414103000 9.163814000 -19.804822000 6 15.460628000 19.043114000
14.561488000 8.993719000 -18.276656000 6 14.406129000 20.105560000
14.769802000 7.462319000 -18.108858000 8 14.814227000 17.726869000
15.538287000 7.113167000 -19.377362000 1 15.654982000 15.804480000
15.619183000 5.641528000 -19.717761000 1 17.023838000 16.849386000
14.811023000 7.885854000 -20.410191000 8 17.891465000 17.006016000
15.049588000 9.983433000 -20.146167000 1 15.772974000 18.936490000
13.691428000 9.387736000 -17.744037000 1 16.055008000 19.333596000
15.802377000 9.637940000 -17.869421000 1 14.864103000 21.094556000
16.221734000 8.942425000 -17.270454000 1 13.604827000 19.987507000
13.836795000 6.899672000 -18.068489000 8 17.495564000 19.696267000
16.546961000 7.509248000 -19.281055000 7 13.802155000 12.818599000
56


6
7
7
6
6
6
8
7
6
7
1
1
1
1
15
8
8
8
6
6
6
6
6
8
1
1
8
1
1
1
1
8
7
6
8
14.935825000 12.912974000 -21.775228000 7 13.284741000 10.470066000
15.747098000 11.831541000 -21.731065000 6 11.999942000 10.134140000
15.260646000 14.023507000 -21.097385000 7 11.090755000 11.103641000
14.413131000 15.046365000 -21.329265000 6 11.670627000 8.778141000
13.274852000 15.065797000 -22.141755000 6 12.673672000 7.869823000
12.870787000 13.854448000 -22.760229000 1 11.370355000 12.084113000
11.825265000 13.643589000 -23.435585000 1 10.104733000 10.877774000
12.707594000 16.350195000 -22.148109000 1 10.672165000 8.434217000
13.474180000 17.077428000 -21.347307000 1 12.477088000 6.825889000
14.520419000 16.314966000 -20.800551000 15 13.358811000 4.532717000
13.604665000 11.907211000 -23.070274000 8 12.890866000 3.132819000
15.684373000 11.106632000 -22.472383000 8 12.366772000 5.635307000
16.634752000 11.963651000 -21.257519000 8 18.495450000 18.675600000
13.404518000 18.132463000 -21.146343000 6 18.586228000 14.984899000
13.298062000 21.344259000 -21.514934000 6 19.704272000 15.317031000
14.110670000 22.520286000 -21.075516000 6 20.083256000 16.766216000
13.021855000 20.951103000 -22.930023000 6 19.939409000 16.740578000
12.103685000 4.981024000 -24.752968000 6 19.638588000 18.081312000
15.113970000 7.295747000 -24.378389000 8 18.804060000 15.819214000
15.378494000 6.619547000 -23.032477000 1 18.600115000 13.923638000
14.319423000 5.506274000 -23.078488000 1 19.375274000 15.193457000
14.509811000 4.950428000 -24.494896000 8 20.850118000 14.494949000
13.319071000 4.252322000 -25.128736000 1 21.616779000 15.142997000
14.760713000 6.206783000 -25.283399000 1 19.423879000 17.517969000
15.946661000 7.861443000 -24.785846000 1 20.854915000 16.318737000
15.266705000 7.294625000 -22.187146000 1 20.510397000 18.735301000
16.663838000 5.910599000 -23.030364000 1 19.360806000 17.939977000
13.329771000 5.943681000 -22.988733000 8 21.501158000 17.001278000
15.406761000 4.331264000 -24.534387000 1 21.594022000 17.320639000
13.273468000 3.221548000 -24.763984000 7 14.505044000 13.036725000
13.431598000 4.277240000 -26.215852000 6 15.657866000 12.453185000
14.465904000 4.494632000 -22.058813000 7 16.671521000 13.061125000
13.974942000 8.239403000 -24.240028000 6 16.435374000 14.377172000
14.285179000 9.563839000 -23.898919000 6 15.288041000 15.091150000
15.497936000 9.846898000 -23.623908000 6 14.260549000 14.359677000
57


7
7
6
7
1
1
1
1
15
8
8
1
8
6
6
6
6
6
8
1
1
8
1
1
1
1
1
8
7
6
8
7
6
8
6
13.084291000 14.875768000 -25.780454000 1 9.702298000 11.258186000 -28.226317000
15.407877000 16.436839000 -24.401201000 6 11.220032000 9.784021000 -28.421385000
16.602495000 16.532809000 -23.822246000 1 13.451561000 12.030537000 -26.353429000
17.266949000 15.297589000 -23.799702000 1 10.638650000 9.064059000 -28.988934000
15.731769000 11.395407000 -25.446246000 15 10.746184000 5.030262000 -25.716769000
12.848404000 15.813020000 -25.471296000 8 10.019039000 3.724935000 -25.652784000
12.335547000 14.236558000 -26.103876000 8 10.104770000 6.352077000 -25.391349000
17.060582000 17.416368000 -23.403310000 6 17.939704000 17.608050000 -18.096811000
18.003534000 20.164567000 -21.894114000 1 18.170428000 18.673635000 -18.178838000
19.198347000 21.038766000 -21.679257000 1 16.976087000 17.476205000 -17.588655000
16.812010000 20.529962000 -22.726800000 6 19.675150000 17.155533000 -16.216551000
8.583471000 7.500096000 -29.715411000 6 19.023391000 16.857948000 -17.383251000
9.487395000 7.465859000 -29.306122000 16 19.560535000 15.339294000 -18.054692000
13.096688000 8.123833000 -28.619323000 6 20.668438000 15.105455000 -16.735157000
13.043146000 7.047336000 -27.532672000 6 20.624418000 16.143009000 -15.840785000
11.650588000 6.449646000 -27.779543000 1 19.490960000 18.054141000 -15.643409000
11.621075000 6.376690000 -29.305654000 1 21.300886000 14.231564000 -16.695965000
10.233597000 6.356263000 -29.905949000 1 21.239749000 16.198238000 -14.953467000
12.304218000 7.635221000 -29.734220000 6 17.853267000 6.791634000 -23.066534000
14.125649000 8.325080000 -28.915626000 1 18.675660000 6.112697000 -23.303413000
13.140896000 7.505074000 -26.558935000 1 17.762513000 7.518461000 -23.880832000
14.066807000 6.056411000 -27.784705000 6 17.545931000 8.732478000 -21.413161000
14.603311000 6.053282000 -26.928722000 6 18.106704000 7.537694000 -21.791108000
10.879746000 7.128274000 -27.419929000 16 19.149619000 6.906912000 -20.537133000
12.206829000 5.511447000 -29.627402000 6 18.828856000 8.274547000 -19.517800000
9.781084000 5.387403000 -29.659064000 6 17.954938000 9.155661000 -20.106113000
10.304009000 6.455252000 -30.995758000 1 16.841766000 9.245222000 -22.052104000
11.446948000 5.127879000 -27.217168000 1 19.270260000 8.344983000 -18.535272000
12.502464000 9.396019000 -28.111352000 1 17.534217000 9.997621000 -19.577098000
13.323781000 10.167218000 -27.269825000 5 B3LYP/6-31G* opt EmpiricalDispersion=GD3
14.439071000 9.747748000 -26.887091000 SCRF(PCM) nosymm scf=xqc
12.803472000 11.386631000 -26.923209000 8 5.304315000 -4.744259000 -3.129358000
11.534440000 11.876076000 -27.222718000 6 7.978655000 -3.742235000 -0.694463000
11.186502000 13.025685000 -26.842758000 6 6.926338000 -3.793167000 0.423026000
10.712606000 10.965161000 -27.988565000 6 5.763719000 -4.530505000 -0.265390000
58


6
6
8
1
1
8
1
1
1
1
1
8
7
6
8
7
6
7
6
6
1
1
1
1
8
6
6
6
6
6
8
1
1
8
1
6.499761000 -5.500663000 -1.196249000 1 3.022089000 -1.026645000
5.730125000 -5.913487000 -2.434560000 1 5.192821000 -1.567727000
7.719192000 -4.825256000 -1.564910000 1 3.897331000 -3.516757000
8.981488000 -3.827553000 -0.271614000 1 5.528407000 -3.659583000
6.667808000 -2.798341000 0.789451000 8 2.917277000 -0.623960000
7.439937000 -4.596248000 1.482077000 7 6.035618000 3.050751000
6.698284000 -5.167864000 1.756120000 6 6.338555000 3.354030000
5.138643000 -3.845015000 -0.842924000 7 6.842807000 4.595516000
6.752635000 -6.405636000 -0.628001000 7 6.214037000 2.486936000
4.873012000 -6.519562000 -2.106079000 6 5.749219000 1.287001000
6.373284000 -6.542263000 -3.066248000 6 5.394738000 0.887345000
4.986595000 -5.273693000 0.668522000 6 5.469380000 1.840874000
7.947339000 -2.468614000 -1.457722000 8 5.111552000 1.734743000
8.556411000 -1.344684000 -0.835563000 7 4.896932000 -0.405679000
8.971928000 -1.471619000 0.322878000 6 4.950484000 -0.775589000
8.651097000 -0.186684000 -1.548906000 7 5.469513000 0.207780000
8.152530000 -0.123292000 -2.780026000 1 6.058914000 3.787499000
8.306182000 1.050403000 -3.459250000 1 6.621854000 5.351429000
7.509795000 -1.226788000 -3.418771000 1 6.855389000 4.858243000
7.433913000 -2.388777000 -2.714843000 1 4.601288000 -1.709685000
8.573672000 1.849440000 -2.898071000 15 3.517878000 -4.646223000
7.643859000 1.254860000 -4.197295000 8 3.048617000 -5.552902000
7.093211000 -1.147523000 -4.414802000 8 2.696642000 -4.303274000
6.961875000 -3.285347000 -3.097369000 8 1.135336000 1.028510000
4.007163000 -3.189764000 1.773075000 6 1.564389000 4.550024000
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61


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63


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1 -9.076164000 2.073818000 -2.983717000 1 2.896326000 5.143997000 -2.096631000
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8 2.967438000 6.626103000 -3.631989000 1 7.183448000 -5.027359000 0.002039000
64


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24.444391000 22.590167000 -1.473463000 6 16.065598000 25.872421000
71


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15.918920000 24.857716000 -6.097606000 7 11.609890000 24.493182000
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14.697842000 29.851383000 -8.266762000 6 15.638330000 24.692858000
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16.921703000 30.473075000 -7.363073000 1 15.882562000 22.570143000
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19.014614000 28.947885000 -8.311707000 6 21.990518000 18.737591000
11.522946000 26.571618000 -6.121492000 16 21.935699000 19.495625000
12.009800000 27.819898000 -5.984762000 6 22.241506000 17.977659000
13.034545000 28.392857000 -6.622718000 6 22.371753000 16.956842000
13.584697000 27.556028000 -7.517775000 1 22.327802000 16.742484000
13.174078000 26.245518000 -7.795405000 1 22.325346000 17.937695000
12.094886000 25.755646000 -7.032336000 1 22.579950000 15.931242000
72


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16 24.920771000 14.374362000 3.060279000 7 33.613109000 13.421621000 -10.839357000
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16 27.307959000 9.130766000 0.697489000 1 33.579369000 15.337273000 -10.021182000
6 25.760332000 9.155027000 -0.093289000 8 30.031329000 15.786988000 -13.845319000
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SCRF(PCM) nosymm scf=xqc 8 30.339288000 13.225195000 -12.757204000
8 33.193965000 17.440126000 -10.992998000 1 30.092179000 11.924082000 -11.185406000
6 34.378316000 13.828943000 -12.048257000 1 27.471540000 12.794229000 -11.206943000
6 33.461348000 13.974682000 -13.269500000 8 27.951718000 11.323432000 -12.574449000
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1 35.143873000 13.068465000 -12.212603000 8 27.004313000 13.473840000 -14.066753000
1 32.612950000 13.289503000 -13.230653000 7 28.703914000 13.736703000 -6.744322000
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1 33.801476000 14.262188000 -15.151161000 7 28.091579000 11.483134000 -6.787267000
73


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28.881179000 12.483773000 -8.743881000 6 25.911509000 16.087396000
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74


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75


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32.363893000 17.554368000 -11.516512000 6 28.036098000 10.259053000 -11.607590000
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11.686379000 19.631425000 -4.904527000 7:8 B3LYP/6-31G* opt EmpiricalDispersion=GD3
12.476928000 19.413466000 -4.195273000 SCRF(PCM) nosymm scf=xqc
18.245332000 10.098785000 -4.145102000 8 6.904432000 -8.452132000 -5.706569000
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76


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8.513269000 1.653939000 -1.477965000 6 6.716671000 -4.519343000
7.780429000 1.809676000 -2.657452000 7 7.241506000 -3.706284000
7.667291000 0.683065000 -3.524721000 1 4.724808000 0.500774000
7.004774000 0.579650000 -4.572933000 1 5.425672000 1.468921000
7.204322000 3.072826000 -2.713260000 1 6.623815000 0.636104000
7.564450000 3.650906000 -1.591869000 1 7.015385000 -5.553386000
8.358933000 2.835505000 -0.794929000 15 7.318606000 -8.979162000
8.375098000 -1.274373000 -3.628614000 8 7.634034000 -10.135593000
9.950858000 -2.313251000 -2.344971000 8 6.005299000 -8.787569000
77


8
6
6
6
6
6
8
1
1
8
1
1
1
1
8
7
6
8
7
6
7
6
6
1
1
1
1
15
8
8
8
6
6
6
6
3.414657000 7.804525000 -3.095923000 6 6.110453000 -4.219050000
3.662943000 5.385311000 -0.301598000 8 5.765147000 -2.253934000
5.044549000 5.889712000 0.150272000 1 5.123924000 -0.417066000
5.191960000 7.116031000 -0.770766000 1 2.857970000 -0.949580000
3.772908000 7.692341000 -0.730657000 8 4.517601000 -0.191171000
3.317451000 8.557919000 -1.889684000 1 3.530398000 -3.298194000
2.932021000 6.523353000 -0.678496000 1 6.209606000 -2.203116000
3.125937000 4.864922000 0.483050000 1 5.966793000 -4.621435000
5.819019000 5.132437000 0.026809000 1 7.180913000 -4.229037000
5.024321000 6.354165000 1.493750000 8 3.880132000 -2.666093000
5.416055000 6.770560000 -1.786512000 7 1.659702000 0.142776000
3.655200000 8.263447000 0.199773000 6 2.109136000 0.763047000
3.947980000 9.455107000 -1.939248000 7 2.861541000 0.245034000
2.278571000 8.855464000 -1.711815000 6 3.125949000 -1.051153000
6.136404000 8.080745000 -0.355404000 6 2.695721000 -1.835689000
3.756275000 4.415098000 -1.427468000 6 1.944089000 -1.160541000
4.085837000 3.100569000 -1.064767000 7 1.494183000 -1.734542000
4.444409000 2.897194000 0.113741000 7 3.188635000 -3.128799000
3.991966000 2.122789000 -1.991396000 6 3.905776000 -3.113406000
3.615351000 2.400413000 -3.249181000 7 3.906764000 -1.878209000
3.515213000 1.373149000 -4.102277000 1 1.833538000 1.808395000
3.334104000 3.743618000 -3.659289000 1 2.005925000 -2.541391000
3.415664000 4.716265000 -2.712152000 1 1.148290000 -1.100067000
3.695274000 0.412782000 -3.789459000 1 4.441267000 -3.950658000
3.172678000 1.520957000 -5.039654000 15 5.949605000 -6.535254000
3.059532000 3.995371000 -4.675852000 8 6.158073000 -7.266281000
3.227423000 5.758921000 -2.928995000 8 5.096039000 -7.054334000
7.686840000 7.974099000 -0.960305000 8 -1.602235000 6.070142000
8.419576000 9.140812000 -0.364537000 6 -0.852002000 5.329847000
7.637928000 7.685860000 -2.433469000 6 0.328700000 6.308992000
5.396221000 -4.995972000 3.880537000 6 0.242819000 6.926427000
4.714147000 -1.365782000 3.186457000 6 -1.271235000 7.123695000
3.905693000 -1.186187000 4.485077000 6 -1.873031000 7.251488000
4.129882000 -2.565282000 5.122683000 8 -1.812181000 5.947345000
5.608938000 -2.793814000 4.815170000 1 -1.287649000 5.114942000
78


1
8
1
1
1
1
8
7
6
8
7
6
8
6
1
6
1
1
15
8
8
8
6
6
6
6
6
8
1
1
8
1
1
1
1
1.266711000 5.809334000 -1.926109000 8 -1.087464000 0.603752000
0.069102000 7.339883000 -1.202488000 7 -1.744914000 0.886399000
0.584705000 6.189444000 -4.280164000 6 -1.710051000 1.971847000
-1.555150000 8.010484000 -3.091627000 7 -2.347964000 3.086022000
-1.441633000 8.133729000 -5.546267000 7 -1.127558000 1.940998000
-2.955540000 7.391543000 -4.959974000 6 -0.622190000 0.726545000
0.929783000 8.148184000 -3.724278000 6 -0.634970000 -0.440531000
-0.451062000 4.008418000 -2.766090000 6 -1.220164000 -0.387088000
0.198458000 3.149231000 -1.881513000 8 -1.301714000 -1.303072000
0.521498000 3.508009000 -0.746126000 7 -0.055757000 -1.487262000
0.446218000 1.891097000 -2.366488000 6 0.296784000 -0.965649000
0.146790000 1.404360000 -3.635810000 7 -0.004870000 0.385256000
0.431314000 0.238047000 -3.940848000 1 -2.185292000 0.992100000
-0.487972000 2.370436000 -4.505337000 1 -2.719130000 3.175599000
-0.747013000 2.086403000 -5.516503000 1 -2.196391000 3.926606000
-0.766321000 3.614155000 -4.043456000 1 0.750972000 -1.489248000
0.901737000 1.225896000 -1.697048000 15 2.337315000 -3.082808000
-1.239591000 4.368863000 -4.658973000 8 2.433423000 -3.294179000
2.453034000 8.151357000 -4.405227000 8 1.756722000 -4.087821000
2.680440000 9.566806000 -4.847726000 8 -5.385524000 2.405954000
2.610688000 6.956920000 -5.305114000 6 -5.241391000 3.655543000
1.533670000 -1.665923000 6.672730000 6 -4.360748000 4.823983000
0.135746000 1.306521000 4.929558000 6 -4.419330000 4.625379000
-1.070641000 1.239605000 5.891053000 6 -5.900250000 4.283969000
-0.519702000 0.349410000 7.025969000 6 -6.260849000 3.522631000
0.985040000 0.638412000 7.028537000 8 -6.222378000 3.484089000
1.868189000 -0.517028000 7.450501000 1 -5.719970000 3.851143000
1.300832000 1.000754000 5.666186000 1 -3.358931000 4.773575000
0.221107000 2.300302000 4.489369000 8 -4.969998000 6.073436000
-1.927675000 0.783505000 5.398984000 1 -3.816964000 3.749523000
-1.551709000 2.512530000 6.282593000 1 -6.490818000 5.208221000
-0.667789000 -0.697151000 6.741770000 1 -6.158309000 4.196768000
1.197397000 1.490017000 7.688158000 1 -7.306848000 3.202098000
1.706483000 -0.717636000 8.516503000 8 -4.022845000 5.736662000
2.919532000 -0.252283000 7.289054000 7 -4.452327000 2.400697000
79


6
8
7
6
7
6
6
1
1
1
1
15
8
8
8
6
6
6
6
6
8
1
1
8
1
1
1
1
8
7
6
8
7
6
7
-3.635844000 2.306539000 -2.570112000 6 -2.983452000 -2.042983000
-3.535267000 3.312793000 -1.836088000 6 -3.842866000 -1.207973000
-3.003726000 1.138164000 -2.312256000 1 -2.724374000 -3.310679000
-3.106017000 0.095004000 -3.158334000 1 -1.511338000 -3.044401000
-2.485539000 -1.043868000 -2.840849000 1 -2.010464000 -2.263685000
-3.855382000 0.207311000 -4.375498000 1 -3.605709000 -0.730466000
-4.530205000 1.365896000 -4.595246000 15 -2.387114000 -0.357015000
-2.042213000 -1.149747000 -1.920397000 8 -2.865041000 0.182545000
-2.680969000 -1.884569000 -3.376408000 8 -2.034011000 -1.797553000
-3.898645000 -0.607436000 -5.085548000 8 -5.655652000 -3.044460000
-5.153179000 1.534019000 -5.461783000 6 -7.492620000 -2.421836000
-2.454027000 5.783992000 -7.207418000 6 -7.314015000 -0.896759000
-2.400826000 6.992092000 -8.095676000 6 -6.786608000 -0.800832000
-2.021387000 4.410200000 -7.634501000 6 -7.579390000 -1.916304000
-3.455950000 0.033667000 7.520469000 6 -6.944986000 -2.511477000
-5.945816000 0.130180000 4.638013000 8 -7.709223000 -2.951552000
-6.992058000 -0.437999000 5.621566000 1 -8.336253000 -2.647398000
-6.227815000 -0.308427000 6.943720000 1 -6.611289000 -0.503488000
-5.505081000 1.027751000 6.765092000 8 -8.598686000 -0.308563000
-4.269627000 1.204758000 7.623063000 1 -5.725537000 -1.063276000
-5.158169000 1.055377000 5.359692000 1 -8.573384000 -1.525911000
-6.417365000 0.623477000 3.786629000 1 -6.836790000 -1.727814000
-7.267431000 -1.459884000 5.365020000 1 -7.600226000 -3.289998000
-8.150299000 0.376258000 5.691685000 8 -6.984406000 0.475860000
-5.484610000 -1.108874000 6.994669000 7 -5.378560000 -3.175084000
-6.201072000 1.850886000 6.972401000 6 -6.704300000 -3.013756000
-4.584603000 1.350548000 8.661346000 7 -7.573720000 -2.876702000
-3.699620000 2.079736000 7.292510000 7 -7.152849000 -3.018456000
-7.006891000 -0.295533000 8.122604000 6 -6.165627000 -3.149889000
-5.068729000 -0.925795000 4.065655000 6 -4.809301000 -3.379449000
-5.514739000 -1.602209000 2.917764000 6 -4.335679000 -3.406096000
-6.707443000 -1.455799000 2.569973000 8 -3.176150000 -3.585770000
-4.629570000 -2.359004000 2.224766000 7 -4.126360000 -3.417174000
-3.375887000 -2.536016000 2.674674000 6 -5.043755000 -3.195768000
-2.497407000 -3.188825000 1.896987000 7 -6.313038000 -3.036944000
80


1
1
1
1
15
8
8
8
6
6
6
6
6
8
1
1
8
1
1
1
1
1
8
7
6
8
7
6
8
6
1
6
1
1
15
-5.099995000 -3.031845000 0.549394000 8 -7.889576000 -1.347647000 10.233343000
-7.244005000 -2.486927000 1.157234000 8 -5.930626000 -2.531562000 8.901384000
-8.512252000 -2.615091000 -0.006167000 8 -3.372348000 -7.250219000 -6.775615000
-4.884880000 -3.169443000 -5.900732000 6 -6.716673000 -7.399401000 -4.683873000
-5.916553000 1.040051000 -8.232594000 6 -7.149470000 -6.170103000 -5.501336000
-6.745197000 1.421003000 -9.426676000 6 -6.052826000 -6.136041000 -6.566081000
-4.728272000 0.126812000 -8.301559000 6 -5.814778000 -7.624349000 -6.839914000
-8.257910000 -2.513220000 7.947128000 6 -4.432423000 -7.957970000 -7.398997000
-9.648240000 -3.696385000 4.633682000 8 -6.016928000 -8.263507000 -5.560369000
-10.504662000 -4.714437000 5.403586000 1 -7.584887000 -7.902491000 -4.248681000
-10.337731000 -4.242716000 6.854773000 1 -7.176590000 -5.268163000 -4.884649000
-10.276995000 -2.715008000 6.675578000 8 -8.417642000 -6.442312000 -6.077642000
-9.550259000 -1.937432000 7.752119000 1 -8.505647000 -5.808522000 -6.811710000
-9.593430000 -2.524876000 5.418384000 1 -5.155733000 -5.689649000 -6.132918000
-10.093131000 -3.488796000 3.660317000 1 -6.584033000 -7.982005000 -7.537398000
-10.163116000 -5.743967000 5.240149000 1 -4.453727000 -7.759835000 -8.480613000
-11.849358000 -4.539167000 4.982732000 1 -4.247517000 -9.028818000 -7.260858000
-12.401885000 -4.743386000 5.758848000 8 -6.446453000 -5.451959000 -7.742696000
-9.392983000 -4.610257000 7.271810000 7 -6.321807000 -6.377276000 0.353545000
-11.302803000 -2.333541000 6.588904000 6 -7.395464000 -6.591264000 -0.427393000
-10.130583000 -1.974901000 8.683565000 7 -7.426617000 -6.826330000 -1.739936000
-9.453660000 -0.892744000 7.436506000 6 -6.186904000 -6.838679000 -2.263057000
-11.449776000 -4.699601000 7.606406000 6 -4.983523000 -6.630763000 -1.577830000
-8.272386000 -4.171701000 4.367812000 6 -5.082653000 -6.372605000 -0.192649000
-8.060368000 -4.820222000 3.148543000 7 -4.011986000 -6.145368000 0.597021000
-8.978490000 -5.058225000 2.366864000 7 -3.902401000 -6.715265000 -2.438023000
-6.756183000 -5.175644000 2.903026000 6 -4.439248000 -6.966627000 -3.611637000
-5.660897000 -4.999458000 3.744319000 7 -5.821648000 -7.053763000 -3.573448000
-4.537808000 -5.389159000 3.398994000 1 -8.350511000 -6.540870000 0.090063000
-5.973420000 -4.357125000 5.001953000 1 -3.176014000 -5.807142000 0.137743000
-5.181023000 -4.179387000 5.716515000 1 -4.171251000 -5.826427000 1.557054000
-7.247137000 -3.976229000 5.263409000 1 -3.901330000 -7.109589000 -4.541238000
-6.592356000 -5.648412000 1.987141000 15 -5.303639000 -4.579834000 -8.592092000
-7.522334000 -3.484237000 6.189524000 8 -5.624412000 -4.767162000 -10.043781000
-7.195741000 -1.723436000 8.957417000 8 -3.936424000 -4.863492000 -8.009935000
81


1
1
1
1
1
6
1
6
16
6
1
6
1
1
6
6
6
16
6
1
6
1
1
6
1
1
6
6
16
6
1
6
1
1
6
11.583462000 4.705059000 2.238785000 1 3.655130000 1.682188000
6.317138000 -8.913720000 -6.324541000 1 3.810225000 1.126501000
-11.366071000 -4.383935000 8.519870000 6 8.678515000 -2.228883000
-3.412699000 -6.338851000 -7.157446000 6 10.033900000 -1.591554000
-8.689424000 -0.474691000 3.857272000 16 11.251092000 -2.019773000
-8.986424000 0.336742000 4.529531000 6 12.288853000 -0.722864000
-10.001709000 0.119369000 4.880377000 1 13.261059000 -0.591278000
-8.951242000 1.648744000 3.795812000 6 11.733489000 -0.021198000
-8.482698000 3.115613000 4.625608000 1 12.234053000 0.801655000
-8.827543000 4.077244000 3.216743000 1 9.841917000 -0.097535000
-8.660916000 5.146409000 3.233731000 6 10.445334000 -0.521448000
-9.272266000 3.305295000 2.178417000 1 8.214183000 -2.034516000
-9.530766000 3.702403000 1.203027000 1 8.046139000 -1.757484000
-9.646545000 1.143587000 1.811493000 6 -8.583861000 1.040037000
-9.335329000 1.914300000 2.508580000 1 -7.867719000 1.643379000
-0.635697000 3.472274000 6.810326000 1 -9.586096000 1.428217000
-1.092315000 4.832874000 6.367316000 6 -8.105940000 0.099143000
-2.144149000 4.990849000 4.979886000 6 -8.281937000 1.123604000
-2.072297000 6.724168000 5.064886000 16 -8.063215000 2.672976000
-2.618342000 7.320007000 4.345847000 6 -7.708182000 1.905148000
-1.285417000 7.145690000 6.101957000 6 -7.766875000 0.544678000
-1.110358000 8.190982000 6.333927000 1 -8.190632000 -0.944704000
-0.074822000 6.188614000 7.707916000 1 -7.480565000 2.507586000
-0.728188000 6.060684000 6.850754000 1 -7.563527000 -0.119245000
0.381273000 3.292241000 6.437410000 6 -4.805852000 6.527480000
-0.601817000 3.402996000 7.905074000 1 -3.859992000 6.169811000
4.318562000 1.150701000 4.813703000 1 -4.748808000 7.619229000
5.618699000 1.889610000 4.700422000 6 -5.804858000 5.390120000
7.057809000 1.147655000 4.020765000 6 -5.909907000 6.134901000
7.941766000 2.645188000 4.114442000 16 -7.555481000 6.690223000
8.960416000 2.693329000 3.750679000 6 -8.071808000 5.919389000
7.176482000 3.640748000 4.651365000 6 -7.034433000 5.277502000
7.536173000 4.653083000 4.801847000 1 -4.879056000 4.912843000
5.097568000 3.852497000 5.424269000 1 -9.105693000 5.983607000
5.854678000 3.206569000 4.991496000 1 -7.140962000 4.743050000
82


6 0.126762000 6.956195000 0.186478000 6 -1.396642000 1.371800000 0.078686000
1 0.234427000 5.870906000 0.282359000 1 -1.364968000 2.457479000 0.104554000
1 1.013420000 7.406115000 0.640338000 1 2.869735000 -1.471251000 0.172331000
6 -1.197661000 8.543862000 1.724240000 1 1.188883000 2.090716000 -0.653712000
6 -1.095530000 7.463590000 0.888405000 1 1.345616000 1.732953000 1.076633000
16 -2.672019000 6.748514000 0.622242000 1 1.951674000 -0.672671000 1.507985000
6 -3.442701000 7.918038000 1.650482000 8 -3.733592000 1.561240000 0.031789000
6 -2.535355000 8.805789000 2.160927000 6 -5.018305000 0.965908000 -0.036497000
1 -0.337940000 9.139418000 2.013860000 1 -5.146809000 0.384283000 -0.959180000
1 -4.512314000 7.876586000 1.809563000 1 -5.209332000 0.314573000 0.827097000
1 -2.806730000 9.620442000 2.823691000 1 -5.732282000 1.791751000 -0.028702000
6 4.815010000 5.343037000 2.495551000 8 -1.658922000 -2.780293000 -0.142069000
1 5.400615000 5.673261000 3.359108000 6 -1.139601000 -3.569581000 0.930974000
1 5.221157000 4.382466000 2.163625000 1 -0.050912000 -3.494602000 0.996667000
6 2.504921000 6.278384000 3.134641000 1 -1.587986000 -3.269507000 1.887701000
6 3.354188000 5.234307000 2.862230000 1 -1.424869000 -4.600232000 0.707566000
16 2.472651000 3.724184000 2.819791000 1* SCF E(RB3LYP) = -689.108444891 au
6 0.969327000 4.530360000 3.147639000 B3LYP/6-31G(d) TD(Root=3,NStates=40) opt
6 1.143843000 5.879749000 3.302560000 6 -0.396609000 -0.749754000 0.302260000
1 2.845499000 7.307897000 3.174532000 6 -1.662270000 -1.382408000 0.343753000
1 0.050407000 3.960588000 3.173778000 6 -2.849505000 -0.605364000 0.251015000
1 0.326853000 6.560339000 3.514258000 1 -3.799664000 -1.073874000 0.469663000
CHAPTER IV 6 -2.699876000 0.769529000 -0.028948000
1 SCF E(RB3LYP) = -689.132338910 au 6 -0.269757000 0.707448000 0.286950000
B3LYP/6-31G(d) opt 6 1.077039000 1.263178000 0.495533000
6 -0.283266000 -0.778090000 0.026854000 8 0.701365000 -1.499965000 0.033671000
6 -1.531439000 -1.418973000 -0.023501000 6 1.991791000 -0.852968000 0.271498000
6 -2.704569000 -0.659381000 -0.024155000 8 2.063603000 0.424147000 -0.217738000
1 -3.643692000 -1.196802000 -0.068940000 6 -1.437957000 1.410982000 -0.059880000
6 -2.641426000 0.737333000 0.026974000 1 -1.401001000 2.449719000 -0.383111000
6 -0.222372000 0.621945000 0.072585000 1 2.713814000 -1.484401000 -0.246456000
6 1.137661000 1.288746000 0.088510000 1 1.180660000 2.277311000 0.102520000
8 0.860996000 -1.547246000 -0.006442000 1 1.429958000 1.259135000 1.553010000
6 2.016787000 -0.838609000 0.418536000 1 2.146894000 -0.881704000 1.366445000
8 2.176317000 0.371551000 -0.256751000 8 -3.748787000 1.589234000 -0.305538000
83


6 -5.056804000 1.034158000 -0.378973000 1 3.487577000 -2.354334000 -0.693304000
1 -5.092043000 0.198639000 -1.087394000 1 4.701159000 -1.751642000 0.471938000
1 -5.396873000 0.689995000 0.605493000 1 -2.232618000 -0.291897000 1.684557000
1 -5.704460000 1.842226000 -0.723406000 2 SCF E(RB3LYP) = -998.817664656 au
8 -1.869444000 -2.725583000 0.338428000 B3LYP/6-31G(d) opt
6 -0.889157000 -3.634787000 0.843174000 6 7.125842000 -8.301871000 -2.075710000
1 -0.114848000 -3.836828000 0.099463000 6 8.169664000 -7.695613000 -1.335773000
1 -0.423412000 -3.242064000 1.753743000 6 9.014905000 -8.489080000 -0.569731000
1 -1.435972000 -4.552964000 1.070317000 1 9.825406000 -8.065819000 0.010266000
-H- SCF E(RB3LYP) = -689.064976775 au 6 8.830827000 -9.883212000 -0.523138000
B3LYP/6-31G* opt= =(noeigentest,TS,verytight,calcall) 6 6.954621000 -9.679007000 -2.030882000
int(grid=ultraflne) 6 5.831223000 -10.288068000 -2.836552000
6 -0.952742000 0.304233000 -0.398263000 8 6.326668000 -7.480365000 -2.833081000
6 0.036951000 1.337836000 -0.152516000 6 5.088532000 -8.066666000 -3.241117000
6 1.354104000 0.991522000 0.030320000 6 4.054400000 -8.002607000 -2.111903000
1 2.119457000 1.735554000 0.218759000 1 4.412105000 -8.568342000 -1.243827000
6 1.777732000 -0.375094000 0.020080000 1 3.140795000 -8.496732000 -2.465256000
6 -0.482300000 -1.054373000 -0.483444000 8 5.276277000 -9.358981000 -3.766308000
6 -1.466934000 -2.000514000 -0.785115000 6 7.804934000 -10.479944000 -1.247728000
8 -2.210267000 0.554731000 -0.420341000 1 7.650785000 -11.553424000 -1.230843000
6 -2.996208000 -0.630130000 0.967871000 1 4.764624000 -7.458702000 -4.089900000
8 -2.991958000 -1.808453000 0.534094000 6 3.744380000 -6.555747000 -1.679935000
6 0.882354000 -1.390400000 -0.202008000 1 4.678884000 -6.078634000 -1.365247000
1 1.185309000 -2.430433000 -0.232790000 1 3.379619000 -5.991617000 -2.549041000
1 -3.934302000 -0.062350000 0.971766000 6 2.721526000 -6.492722000 -0.565444000
1 -2.276491000 -1.718643000 -1.443711000 6 1.350553000 -6.424063000 -0.847746000
1 -1.254567000 -3.062545000 -0.704420000 6 3.121347000 -6.538333000 0.777151000
8 -0.462027000 2.597801000 -0.116802000 1 1.021116000 -6.380259000 -1.884104000
6 0.448085000 3.662658000 0.107422000 1 4.182080000 -6.584516000 1.015479000
1 0.945340000 3.567169000 1.082120000 6 0.405423000 -6.404727000 0.178850000
1 1.210683000 3.711222000 -0.681363000 6 2.180635000 -6.519928000 1.807693000
1 -0.149701000 4.575409000 0.091982000 1 -0.653000000 -6.347052000 -0.062475000
8 3.118305000 -0.526870000 0.243430000 1 2.512572000 -6.552352000 2.842388000
6 3.632702000 -1.847472000 0.270296000 6 0.817929000 -6.453624000 1.511624000
1 3.163269000 -2.444789000 1.063554000 1 0.083812000 -6.435525000 2.312797000
84


1 6.197283000 -11.120795000 -3.446180000 6 1.294365000 -6.313938000 -1.013254000
1 5.046110000 -10.688665000 -2.174630000 6 3.012922000 -6.365873000 0.749233000
8 8.252285000 -6.340417000 -1.438736000 1 1.026576000 -6.325043000 -2.064552000
6 9.296472000 -5.685645000 -0.737171000 1 4.056192000 -6.413967000 1.041770000
1 9.211786000 -5.837476000 0.347247000 6 0.315592000 -6.197975000 -0.055112000
1 10.283920000 -6.029853000 -1.071849000 6 2.032619000 -6.248050000 1.707611000
1 9.187019000 -4.623495000 -0.963501000 1 -0.726153000 -6.123748000 -0.347979000
8 9.724983000 -10.554147000 0.268448000 1 2.302581000 -6.213790000 2.757272000
6 9.606096000 -11.962967000 0.355006000 6 0.673448000 -6.164807000 1.317924000
1 8.636218000 -12.262761000 0.775145000 1 -0.099556000 -6.069767000 2.073364000
1 9.734185000 -12.440961000 -0.625788000 1 6.030187000 -11.286736000 -3.110368000
1 10.404592000 -12.292113000 1.022921000 1 4.942748000 -10.665696000 -1.862120000
2* SCF E(RB3LYP) = -998.764608402 au (not fully 8 7.998734000 -6.519657000 -0.785957000
converged) 6 9.134390000 -5.839998000 -0.314091000
B3LYP/6-31G(d) TD(Root=5) opt 1 9.594064000 -6.351158000 0.546704000
6 7.113385000 -8.392141000 -1.974276000 1 9.901497000 -5.734317000 -1.097004000
6 8.273875000 -7.757354000 -1.450948000 1 8.805394000 -4.842722000 -0.001782000
6 9.400656000 -8.611617000 -1.194323000 8 10.154512000 -10.639047000 -0.236726000
1 10.420314000 -8.256288000 -1.079653000 6 9.904541000 -11.941359000 0.247779000
6 9.131134000 -9.963112000 -0.873506000 1 9.083708000 -11.942097000 0.977964000
6 6.914533000 -9.752923000 -1.852029000 1 9.660237000 -12.635992000 -0.568202000
6 5.744344000 -10.377876000 -2.567131000 1 10.829548000 -12.267426000 0.730683000
8 6.206816000 -7.570629000 -2.665087000 K3 -H- SCF E(RB3LYP) = -998.760865860 au
6 5.020175000 -8.185370000 -3.138468000 B3LYP/6-31G* opt=(noeigentest,TS, calcall)
6 3.922880000 -8.040768000 -2.071981000 int(grid=ultrafine)
1 4.168678000 -8.644599000 -1.192831000 6 1.420044000 0.432481000 0.947452000
1 2.991176000 -8.452800000 -2.483396000 6 1.557358000 -1.011521000 0.815399000
8 5.203265000 -9.493999000 -3.566431000 6 2.636100000 -1.544247000 0.155439000
6 7.908407000 -10.552600000 -1.189704000 1 2.770827000 -2.614459000 0.047933000
1 7.708975000 -11.593830000 -0.959258000 6 3.622453000 -0.709028000 -0.459258000
1 4.763704000 -7.615284000 -4.037993000 6 2.457912000 1.242636000 0.356506000
6 3.736010000 -6.558399000 -1.673591000 6 2.253265000 2.624109000 0.457729000
1 4.689920000 -6.168345000 -1.306505000 8 0.392258000 0.967320000 1.474127000
1 3.480509000 -5.970012000 -2.564638000 6 -0.389630000 2.486489000 0.180046000
6 2.672527000 -6.405720000 -0.639988000 6 -1.535424000 1.684946000 -0.389031000
85


1 -1.107742000 0.854033000 -0.960576000 6 7.569073000 -7.931102000 -0.774979000
1 -2.055016000 2.323121000 -1.120350000 6 8.363353000 -8.624495000 0.125107000
8 0.582910000 2.792267000 -0.553244000 1 8.987143000 -8.100390000 0.842120000
6 3.528806000 0.657188000 -0.392822000 6 8.370677000 -10.029157000 0.128435000
1 4.264970000 1.306828000 -0.852159000 6 6.784044000 -10.027263000 -1.708808000
1 -0.561284000 3.027047000 1.121499000 6 5.944599000 -10.752396000 -2.739049000
6 -2.530944000 1.174716000 0.670260000 8 5.994709000 -7.903859000 -2.561596000
1 -1.957700000 0.641831000 1.433889000 6 4.973493000 -8.679992000 -3.168987000
1 -3.014114000 2.031070000 1.158909000 8 5.465353000 -9.856250000 -3.741666000
6 -3.579548000 0.260987000 0.074491000 6 7.583194000 -10.724035000 -0.790938000
6 -4.824543000 0.747024000 -0.344145000 1 7.586392000 -11.809185000 -0.818325000
6 -3.302853000 -1.103048000 -0.099097000 1 4.559266000 -8.069754000 -3.971697000
1 -5.058599000 1.801494000 -0.210663000 1 6.536382000 -11.504146000 -3.270975000
1 -2.340320000 -1.490495000 0.229423000 1 5.095068000 -11.272075000 -2.263634000
6 -5.769350000 -0.103054000 -0.922187000 8 9.183943000 -10.614353000 1.061563000
6 -4.243297000 -1.955674000 -0.677247000 6 9.235959000 -12.028931000 1.107813000
1 -6.731803000 0.292918000 -1.236578000 1 8.251689000 -12.464178000 1.329542000
1 -4.012874000 -3.011131000 -0.800155000 1 9.610484000 -12.452456000 0.165636000
6 -5.480936000 -1.457971000 -1.091585000 1 9.928734000 -12.278653000 1.913758000
1 -6.215934000 -2.122056000 -1.538893000 1 7.548908000 -6.845817000 -0.785689000
1 1.770688000 3.023587000 1.341930000 1 4.203203000 -8.908037000 -2.412216000
1 2.891576000 3.310801000 -0.090239000 3* SCF E(RB3LYP) = -574.609623453 au
8 0.551292000 -1.724468000 1.388735000 B3LYP/6-31G(d) TD(Root=4,NStates=40) opt
6 0.650020000 -3.139609000 1.360409000 6 -0.915137000 0.818939000 0.017728000
1 0.647876000 -3.523267000 0.331195000 6 -0.037374000 1.921416000 -0.045901000
1 1.558647000 -3.486904000 1.870074000 6 1.359119000 1.665842000 -0.089557000
1 -0.228773000 -3.512552000 1.889262000 1 2.094048000 2.460795000 -0.078330000
8 4.613781000 -1.414639000 -1.086880000 6 1.804877000 0.318957000 -0.043440000
6 5.625049000 -0.673800000 -1.746598000 6 -0.479607000 -0.541486000 0.024955000
1 5.206804000 -0.044858000 -2.544280000 6 -1.490930000 -1.636008000 0.006703000
1 6.180183000 -0.037343000 -1.043911000 8 -2.238239000 1.106215000 0.057501000
1 6.303771000 -1.409240000 -2.182779000 6 -3.114481000 -0.012146000 0.317641000
3 SCF E(RB3LYP) = -574.617063687 au 8 -2.774903000 -1.135368000 -0.406749000
B3LYP/6-31G* opt 6 0.925430000 -0.791278000 0.031094000
6 6.771574000 -8.630894000 -1.687862000 1 1.291912000 -1.808096000 -0.039709000
86


1 1 -4.104065000 -1.227645000 0.319581000 -2.427778000 0.001992000 -0.710065000 B3LYP/6-31G* opt 6 7.160767000 -8.305395000 -2.046828000
1 -1.618873000 -2.132484000 0.994247000 6 8.229245000 -7.724644000 -1.351909000
8 3.152485000 0.183947000 -0.078455000 6 9.089001000 -8.519356000 -0.609782000
6 3.742159000 -1.107137000 0.045024000 1 9.922243000 -8.086979000 -0.065016000
1 3.416422000 -1.598750000 0.967909000 6 8.893670000 -9.908930000 -0.546848000
1 3.487910000 -1.736061000 -0.815864000 6 6.965531000 -9.686817000 -2.005263000
1 4.819665000 -0.939287000 0.070637000 6 5.820187000 -10.281559000 -2.789510000
1 -0.444747000 2.924232000 -0.017941000 8 6.343702000 -7.472948000 -2.776147000
1 -3.088346000 -0.196727000 1.404729000 6 5.102800000 -8.052911000 -3.194005000
-H- M SCF E(RB3LYP) = -574.550443962 au 6 4.063333000 -7.989064000 -2.069626000
B3LYP/6-31G* opt= =(noeigentest,TS, calcall) 1 4.429122000 -8.532615000 -1.190801000
6 0.972665000 -0.890417000 0.331878000 1 3.161530000 -8.507408000 -2.418535000
6 0.022083000 -1.925563000 0.024779000 8 5.286368000 -9.342775000 -3.723343000
6 -1.303026000 -1.628851000 -0.131363000 6 7.833720000 -10.486143000 -1.247453000
1 -2.028936000 -2.405104000 -0.358238000 1 7.670299000 -11.559116000 -1.226115000
6 -1.792094000 -0.286330000 -0.036372000 1 4.785114000 -7.439795000 -4.041586000
6 0.453748000 0.453183000 0.508516000 6 3.718566000 -6.542061000 -1.665794000
6 1.384254000 1.438531000 0.825457000 1 4.637307000 -6.038560000 -1.345622000
8 2.229810000 -1.117761000 0.377489000 1 3.354422000 -6.000537000 -2.549359000
6 3.290383000 0.274316000 -0.646712000 6 2.680297000 -6.479062000 -0.565443000
8 2.557280000 1.268000000 -0.846544000 6 1.312776000 -6.427466000 -0.866701000
6 -0.927022000 0.739261000 0.251847000 6 3.063232000 -6.504593000 0.782580000
1 -1.268320000 1.765065000 0.339843000 1 0.996628000 -6.399388000 -1.907687000
1 3.458387000 -0.440260000 -1.461537000 1 4.121066000 -6.537255000 1.035635000
1 1.105610000 2.488131000 0.808037000 6 0.354134000 -6.404313000 0.147248000
1 2.259553000 1.184777000 1.410005000 6 2.108952000 -6.482442000 1.800390000
8 -3.136804000 -0.167988000 -0.250883000 1 -0.701455000 -6.359398000 -0.108551000
6 -3.695900000 1.133638000 -0.206238000 1 2.427648000 -6.498658000 2.839563000
1 -3.570957000 1.590796000 0.784964000 6 0.749680000 -6.432589000 1.485704000
1 -3.244843000 1.789909000 -0.962866000 1 0.005089000 -6.411075000 2.277019000
1 -4.759942000 1.013486000 -0.417561000 1 6.157476000 -11.129054000 -3.395153000
1 0.393643000 -2.939391000 -0.085372000 1 5.027751000 -10.653247000 -2.119783000
1 4.022980000 0.247986000 0.171472000 8 9.795084000 -10.599722000 0.218460000
4 SCF E(RB3LYP) = -884.299542423 au 6 9.651094000 -12.005441000 0.311195000
87


1 8.685896000 -12.286310000 0.755070000 1 -0.102422000 -6.520897000 2.243314000
1 9.747506000 -12.489055000 -0.670720000 1 5.936578000 -11.232329000 -3.017878000
1 10.458348000 -12.348888000 0.961040000 1 4.951995000 -10.436369000 -1.773411000
1 8.367670000 -6.649302000 -1.407396000 8 10.013722000 -10.636566000 0.008433000
4* SCF E(RB3LYP) = -884.270488349au 6 9.892324000 -12.057692000 0.209865000
B3LYP/6-31G(d) opt TD(root=12,nstates=12) 1 8.986225000 -12.284349000 0.777150000
6 7.222386000 -8.331566000 -1.941024000 1 9.888935000 -12.578097000 -0.751605000
6 8.407705000 -7.757298000 -1.382678000 1 10.773344000 -12.338583000 0.783388000
6 9.312351000 -8.553511000 -0.743617000 1 8.542600000 -6.686378000 -1.470207000
1 10.213910000 -8.153709000 -0.294943000 -H- SCF E(RB3LYP) = -884.238637088 au
6 9.076846000 -9.959095000 -0.639827000 B3LYP/6-31G* opt=(noeigentest,TS, calcall)
6 6.995391000 -9.751751000 -1.861509000 6 1.678847000 -0.708297000 0.209546000
6 5.743500000 -10.281023000 -2.516045000 6 2.556165000 -1.673167000 0.815357000
8 6.376628000 -7.519768000 -2.505574000 6 3.912498000 -1.563707000 0.677649000
6 5.082818000 -8.084224000 -3.065681000 1 4.582916000 -2.293885000 1.123045000
6 3.986638000 -7.917939000 -2.038528000 6 4.511520000 -0.473566000 -0.028950000
1 4.259230000 -8.367089000 -1.076360000 6 2.294662000 0.348842000 -0.564715000
1 3.129343000 -8.485795000 -2.421058000 6 1.417996000 1.275546000 -1.133490000
8 5.343198000 -9.370665000 -3.532733000 8 0.414115000 -0.720340000 0.401616000
6 7.915917000 -10.540396000 -1.214758000 6 -0.283697000 1.161748000 0.958286000
1 7.752083000 -11.609665000 -1.150771000 6 -1.646353000 0.998014000 0.326233000
1 4.939017000 -7.466497000 -3.951728000 1 -1.538345000 0.841711000 -0.752806000
6 3.537297000 -6.462980000 -1.767153000 1 -2.159278000 1.965299000 0.442814000
1 4.423997000 -5.862344000 -1.505102000 8 0.577609000 1.972463000 0.525294000
1 3.127927000 -6.037727000 -2.694663000 6 3.718039000 0.482265000 -0.615717000
6 2.517644000 -6.418565000 -0.652794000 1 4.142522000 1.317799000 -1.161935000
6 1.185848000 -6.189585000 -0.921528000 1 -0.193787000 0.849194000 2.008872000
6 2.960137000 -6.753086000 0.690920000 6 -2.494414000 -0.123470000 0.952941000
1 0.882298000 -5.992282000 -1.952765000 1 -1.951743000 -1.066372000 0.842064000
1 4.007496000 -6.597547000 0.958877000 1 -2.592829000 0.064670000 2.030684000
6 0.189873000 -6.237979000 0.094288000 6 -3.869176000 -0.226994000 0.327749000
6 1.958364000 -6.717346000 1.720008000 6 -4.948106000 0.517052000 0.824135000
1 -0.843815000 -5.992624000 -0.123728000 6 -4.085922000 -1.047542000 -0.787813000
1 2.257912000 -6.898538000 2.753302000 1 -4.801446000 1.153647000 1.694700000
6 0.630561000 -6.493019000 1.437050000 1 -3.261126000 -1.638267000 -1.181129000
88


6 -6.206131000 0.447111000 0.223951000 B3LYP/6-31G(d) TD(Root=5,NStates=40) opt
6 -5.341546000 -1.120852000 -1.392269000 6 7.025388000 -8.172629000 -1.756428000
1 -7.030624000 1.029073000 0.628159000 6 7.986378000 -7.599506000 -0.885249000
1 -5.489151000 -1.767093000 -2.253916000 1 8.057785000 -6.521220000 -0.812577000
6 -6.406868000 -0.372384000 -0.888228000 6 8.756478000 -8.485808000 -0.079141000
1 -7.386542000 -0.431097000 -1.355084000 1 9.513288000 -8.099152000 0.593797000
1 1.796920000 2.193082000 -1.573823000 6 8.505481000 -9.876741000 -0.142506000
1 0.451716000 0.942622000 -1.487345000 1 9.100277000 -10.544062000 0.476688000
8 5.878394000 -0.503827000 -0.047095000 6 6.793370000 -9.578381000 -1.875219000
6 6.549168000 0.556492000 -0.705830000 6 5.869782000 -10.082104000 -2.928825000
1 6.291192000 0.593690000 -1.773156000 8 6.303436000 -7.301790000 -2.499921000
1 6.314792000 1.526728000 -0.247000000 6 5.208098000 -7.880233000 -3.250061000
1 7.616129000 0.352861000 -0.598511000 8 5.563711000 -9.050071000 -3.883124000
1 2.107644000 -2.482570000 1.382847000 6 7.518015000 -10.439754000 -0.988850000
5 SCF E(RB3LYP) = -460.096536748 au 1 7.360674000 -11.512520000 -1.014796000
B3LYP/6-31G(d) opt 1 4.955855000 -7.136306000 -4.005862000
6 7.049476000 -8.170845000 -1.799912000 1 6.311727000 -10.907006000 -3.507012000
6 7.975944000 -7.641839000 -0.896761000 1 4.912898000 -10.466741000 -2.512424000
1 8.116951000 -6.565947000 -0.864474000 1 4.377683000 -8.021391000 -2.538661000
6 8.686636000 -8.498692000 -0.061276000 5* SCF E(RB3LYP) = -460.028626626 au
1 9.404326000 -8.086692000 0.642920000 B3LYP/6-31G* opt=(noeigentest,TS,verytight,calcall)
6 8.477163000 -9.880291000 -0.122664000 6 -0.102079000 -0.752860000 0.343424000
1 9.030876000 10.548654000 0.530210000 6 -1.335249000 -1.425357000 0.037819000
6 6.840432000 -9.554792000 -1.889152000 6 -2.462929000 -0.705793000 -0.264325000
6 5.863795000 10.083610000 -2.917408000 1 -3.387956000 -1.232146000 -0.489463000
8 6.364837000 -7.292570000 -2.602293000 6 -2.455073000 0.721162000 -0.322185000
6 5.225506000 -7.868796000 -3.229399000 6 -0.125831000 0.704895000 0.370158000
8 5.518423000 -9.074413000 -3.867966000 6 1.052329000 1.351563000 0.721806000
6 7.560888000 10.396952000 -1.036897000 8 0.989469000 -1.385976000 0.525686000
1 7.407007000 11.472623000 -1.101056000 6 2.568126000 -0.513345000 -0.476202000
1 4.904632000 -7.158205000 -3.991153000 8 2.228985000 0.636638000 -0.819944000
1 6.305063000 10.899940000 -3.497455000 6 -1.304257000 1.405714000 -0.038042000
1 4.949432000 10.471320000 -2.436891000 1 -1.280991000 2.492730000 -0.069697000
1 4.438938000 -8.009233000 -2.468543000 1 2.548519000 -1.325582000 -1.213332000
5* SCF E(RB3LYP) = -460.089457266 au 1 1.147127000 2.427561000 0.607898000
89


1 1.750604000 0.876456000 1.399431000 1 2.138799000 -6.696106000 2.854078000
1 3.160732000 -0.701017000 0.429418000 6 0.541502000 -6.561299000 1.410681000
1 -1.332025000 -2.510882000 0.044506000 1 -0.247443000 -6.578486000 2.157881000
1 -3.363862000 1.251711000 -0.589411000 1 6.249884000 -11.010710000 -3.344461000
6 SCF E(RB3LYP) = -769.779140373 au 1 5.058993000 -10.579856000 -2.110022000
B3LYP/6-31G(d) opt 6* SCF E(RB3LYP) = -769.759522462 au
6 7.171354000 -8.225351000 -1.846507000 B3LYP/6-31G(d) TD(Root=14,NStates=40) opt
6 8.202882000 -7.654343000 -1.093608000 6 7.234396000 -8.232797000 -1.849140000
1 8.321079000 -6.575187000 -1.106119000 6 8.378811000 -7.824242000 -1.152339000
6 9.047499000 -8.473361000 -0.350389000 1 8.631353000 -6.770736000 -1.136372000
1 9.847429000 -8.027218000 0.234336000 6 9.211430000 -8.775372000 -0.461956000
6 8.868622000 -9.860768000 -0.352269000 1 10.066667000 -8.399913000 0.088292000
1 9.527181000 -10.500294000 0.228079000 6 8.919280000 -10.129600000 -0.480318000
6 6.987603000 -9.614637000 -1.871841000 1 9.530253000 -10.845709000 0.053727000
6 5.881924000 -10.185157000 -2.727028000 6 6.962722000 -9.609706000 -1.914285000
8 6.372674000 -7.376540000 -2.568618000 6 5.816245000 -10.061397000 -2.761796000
6 5.162525000 -7.950930000 -3.083435000 8 6.488303000 -7.316447000 -2.452565000
6 4.062085000 -7.940752000 -2.017232000 6 5.190906000 -7.789724000 -2.993605000
1 4.380210000 -8.523908000 -1.145201000 6 4.124359000 -7.768843000 -1.920870000
1 3.184099000 -8.444747000 -2.440033000 1 4.439093000 -8.340730000 -1.038457000
8 5.390564000 -9.214230000 -3.653116000 1 3.245929000 -8.283508000 -2.326703000
6 7.844354000 -10.419158000 -1.114332000 8 5.405048000 -9.034541000 -3.630593000
1 7.708532000 -11.499056000 -1.132249000 6 7.793991000 -10.539947000 -1.195305000
1 4.888348000 -7.303632000 -3.920541000 1 7.520713000 -11.590427000 -1.224156000
6 3.686841000 -6.515285000 -1.566109000 1 4.988467000 -7.086737000 -3.799755000
1 4.582826000 -6.024596000 -1.170464000 6 3.694675000 -6.357121000 -1.457725000
1 3.370562000 -5.933238000 -2.442258000 1 4.556679000 -5.838191000 -1.018301000
6 2.586919000 -6.507424000 -0.525506000 1 3.407505000 -5.787545000 -2.361395000
6 1.238895000 -6.439757000 -0.902242000 6 2.555677000 -6.422986000 -0.471531000
6 2.891769000 -6.600498000 0.839325000 6 1.277642000 -6.954866000 -0.916553000
1 0.982751000 -6.359456000 -1.956931000 6 2.741722000 -6.073867000 0.851740000
1 3.933313000 -6.646956000 1.150963000 1 1.039733000 -6.977756000 -1.980136000
6 0.223526000 -6.466235000 0.054789000 1 3.721664000 -5.702872000 1.163248000
6 1.880457000 -6.627982000 1.800376000 6 0.229603000 -7.017332000 0.052773000
1 -0.815694000 -6.407651000 -0.258700000 6 1.716123000 -6.204735000 1.824407000
90


1 -0.756109000 -7.363018000 -0.262035000 1 4.740812000 2.095552000 -1.894834000
1 1.863590000 -5.859466000 2.842111000 6 5.628152000 0.516396000 -0.723929000
6 0.430969000 -6.678002000 1.373300000 1 6.617970000 0.638631000 -1.155732000
1 -0.385403000 -6.779520000 2.087165000 1 -2.500741000 -2.083625000 -1.907794000
1 6.111412000 -10.910761000 -3.390600000 1 -1.165596000 -0.843659000 -1.655916000
1 4.999416000 -10.416391000 -2.108977000 1 -2.971179000 2.338404000 1.411084000
6* SCF E(RB3LYP) = -769.716873676 au 1 -6.371295000 0.349457000 -0.368086000
B3LYP/6-31G* opt=(noeigentest,TS,calcall) 9 SCF E(RB3LYP) = -1191.53950741 au
6 -2.477072000 0.657715000 0.136409000 B3LYP/6-31G(d) opt
6 -3.389458000 1.570735000 0.767273000 6 10.783585000 18.582064000 3.454089000
6 -4.741324000 1.457249000 0.559763000 6 8.576035000 19.470596000 3.756137000
1 -5.416662000 2.162628000 1.039196000 6 8.234706000 18.057467000 3.152996000
6 -5.294521000 0.419205000 -0.247260000 6 9.109163000 16.972650000 3.782833000
6 -3.045704000 -0.346548000 -0.748876000 1 10.719795000 18.926574000 2.409316000
6 -2.144363000 -1.207550000 -1.374002000 1 11.798912000 18.733596000 3.828520000
8 -1.224163000 0.663747000 0.379586000 1 7.187483000 17.800614000 3.330063000
6 -0.512331000 -1.289500000 0.788457000 1 8.401531000 18.050783000 2.072629000
6 0.863969000 -1.045912000 0.216041000 8 9.930017000 19.344379000 4.268558000
1 0.786198000 -0.786024000 -0.845247000 8 10.497133000 17.200763000 3.538800000
1 1.386589000 -2.014543000 0.253319000 6 10.476150000 23.871235000 2.165489000
8 -1.354163000 -2.054040000 0.254674000 6 9.604324000 22.759995000 1.938956000
6 -4.462406000 -0.479431000 -0.862757000 6 8.954819000 22.618635000 0.712838000
1 -4.866213000 -1.275360000 -1.484652000 6 9.381050000 21.784511000 2.984874000
1 -0.640852000 -1.068173000 1.858486000 6 8.549844000 20.651204000 2.731415000
6 1.676185000 0.017852000 0.976666000 6 7.758885000 20.637094000 1.546484000
1 1.120319000 0.959019000 0.948002000 6 8.006293000 21.618968000 0.507346000
1 1.750060000 -0.278897000 2.031835000 6 11.065027000 24.070262000 3.382517000
6 3.064262000 0.205483000 0.402358000 6 10.002030000 22.059780000 4.252162000
6 4.132227000 -0.605176000 0.810856000 6 6.658828000 19.742026000 1.303863000
6 3.305430000 1.176894000 -0.578704000 6 7.264469000 21.575488000 -0.715431000
1 3.967083000 -1.359089000 1.578345000 6 6.263499000 20.665736000 -0.910656000
1 2.489486000 1.820267000 -0.901261000 6 5.941999000 19.758014000 0.135170000
6 5.402991000 -0.453734000 0.254562000 1 6.338940000 19.066830000 2.083066000
6 4.574318000 1.332613000 -1.138515000 1 7.504026000 22.310632000 -1.480107000
1 6.218505000 -1.089987000 0.589119000 1 5.698128000 20.651122000 -1.838117000
91


1 5.106032000 19.074163000 0.013501000 8 0.572354000 -2.607694000 3.148368000
6 10.798037000 23.159686000 4.441670000 6 -3.231744000 -1.441124000 -2.378798000
1 10.638487000 24.567407000 1.346022000 6 -2.650489000 -0.658278000 -1.332115000
1 11.715133000 24.924524000 3.550612000 6 -3.376076000 0.380847000 -0.749921000
1 9.819958000 21.400408000 5.086561000 6 -1.302293000 -0.931302000 -0.881350000
1 11.227686000 23.341795000 5.423219000 6 -0.749994000 -0.178198000 0.199081000
6 7.687590000 19.739316000 4.983164000 6 -1.438854000 0.988735000 0.639098000
6 6.455689000 20.394178000 4.825477000 6 -2.792985000 1.237560000 0.181374000
6 8.063520000 19.281503000 6.249671000 6 -2.514037000 -2.415305000 -3.013946000
6 5.607414000 20.577124000 5.921934000 6 -0.585024000 -1.946377000 -1.604230000
6 7.208806000 19.471737000 7.341204000 6 -0.871729000 2.009282000 1.479925000
6 5.985155000 20.109291000 7.188812000 6 -3.520216000 2.370204000 0.666791000
1 9.025433000 18.802893000 6.384248000 6 -2.944757000 3.280252000 1.508434000
1 7.508937000 19.118196000 8.324278000 6 -1.586836000 3.104582000 1.890879000
1 5.313084000 20.267490000 8.026314000 1 0.169708000 1.952791000 1.758480000
1 8.870524000 15.998691000 3.343282000 1 -4.543293000 2.501363000 0.322315000
1 9.156264000 23.332935000 -0.082817000 1 -3.502669000 4.143615000 1.859690000
1 8.921905000 16.909162000 4.863241000 1 -1.101941000 3.856648000 2.507782000
1 6.176185000 20.775852000 3.851978000 6 -1.164280000 -2.646559000 -2.630652000
8 4.396385000 21.205640000 5.860641000 1 -4.256125000 -1.222108000 -2.670707000
6 3.973459000 21.734996000 4.613945000 1 -2.958393000 -2.996293000 -3.817474000
1 4.667203000 22.501207000 4.243912000 1 0.444561000 -2.149120000 -1.353246000
1 3.869482000 20.949433000 3.853693000 1 -0.577068000 -3.388306000 -3.165623000
1 2.998081000 22.189273000 4.798161000 6 1.821308000 -0.299097000 0.060576000
9* SCF E(RB3LYP) = -1191.53950741 au 6 1.890161000 0.960881000 -0.555058000
B3LYP/6-31G(d) TD(NStates=80) 6 2.922542000 -1.157738000 -0.009956000
6 -0.157460000 -2.708616000 1.942379000 6 3.052648000 1.358308000 -1.222841000
6 0.568764000 -0.693743000 0.862155000 6 4.080416000 -0.751842000 -0.682820000
6 0.756446000 -0.291449000 2.372172000 6 4.157513000 0.496893000 -1.284266000
6 1.388344000 -1.436394000 3.164638000 1 2.865291000 -2.142654000 0.436271000
1 -1.145081000 -2.231218000 2.047269000 1 4.931353000 -1.425855000 -0.738668000
1 -0.285678000 -3.770855000 1.720439000 1 5.047136000 0.824546000 -1.812782000
1 1.400041000 0.586760000 2.464574000 1 1.499015000 -1.147195000 4.214812000
1 -0.207269000 -0.047863000 2.827131000 1 -4.402448000 0.556665000 -1.065390000
8 0.539807000 -2.146647000 0.860218000 1 2.387776000 -1.667844000 2.772279000
92


1 1.028263000 1.614994000 -0.527361000 6 9.497720000 22.825079000 5.132312000
8 3.204826000 2.560907000 -1.852109000 1 9.102350000 25.078585000 2.610147000
6 2.109235000 3.462561000 -1.857980000 1 9.565468000 25.000535000 5.042495000
1 1.233484000 3.031244000 -2.360285000 1 9.378430000 20.727414000 4.997285000
1 1.825880000 3.763638000 -0.840647000 1 9.685793000 22.789531000 6.202027000
1 2.447943000 4.340011000 -2.412078000 6 7.847879000 17.448691000 5.652946000
10 SCF E(RB3LYP) = -1191.55577998 au 6 6.609875000 17.604713000 6.296946000
B3LYP/6-31G(d) opt 6 9.030428000 17.570230000 6.382859000
6 9.466303000 16.825587000 2.466827000 6 6.559848000 17.892145000 7.663408000
6 9.005180000 19.110590000 2.970394000 6 8.970756000 17.855623000 7.752572000
6 7.639236000 18.498510000 3.331337000 6 7.751205000 18.019721000 8.394841000
6 7.856044000 17.196331000 4.155492000 1 9.981980000 17.420229000 5.886810000
1 8.650606000 16.488978000 1.800247000 1 9.891315000 17.946254000 8.323327000
1 10.364397000 16.238034000 2.264377000 1 7.688477000 18.237890000 9.456278000
1 7.055151000 19.218977000 3.910895000 1 7.052342000 16.483234000 3.912273000
1 7.075416000 18.290735000 2.415925000 1 8.624945000 23.968060000 0.529128000
8 9.791773000 18.176537000 2.201506000 1 9.551064000 19.254474000 3.904292000
8 9.114475000 16.598825000 3.804925000 1 5.695844000 17.494767000 5.721973000
6 9.171450000 24.127381000 3.132782000 8 5.408381000 18.060244000 8.378585000
6 8.980908000 22.930034000 2.374551000 6 4.169394000 17.948415000 7.698271000
6 8.694963000 22.994646000 1.010516000 1 4.076097000 18.698029000 6.900957000
6 9.075527000 21.639457000 3.024243000 1 4.032100000 16.947162000 7.268257000
6 8.901188000 20.453684000 2.258947000 1 3.397961000 18.125307000 8.450058000
6 8.580558000 20.542691000 0.878511000 10* SCF E(RB3LYP) = -1191.55577998 au
6 8.480066000 21.843690000 0.251563000 B3LYP/6-31G(d) TD(NStates=80)
6 9.425181000 24.084363000 4.475619000 6 0.118323000 -2.948052000 -1.523599000
6 9.331027000 21.654163000 4.438773000 6 -0.455952000 -0.763669000 -0.758007000
6 8.329760000 19.404779000 0.038882000 6 0.440716000 -1.206918000 0.412566000
6 8.151299000 21.942575000 -1.137048000 6 1.721358000 -1.892419000 -0.145959000
6 7.913394000 20.826637000 -1.890140000 1 -0.109146000 -3.634645000 -0.687032000
6 8.003176000 19.542210000 -1.285065000 1 0.035600000 -3.489520000 -2.468452000
1 8.423157000 18.414411000 0.457468000 1 0.711714000 -0.337250000 1.017838000
1 8.089447000 22.934828000 -1.577890000 1 -0.114560000 -1.890367000 1.063418000
1 7.659965000 20.913576000 -2.943166000 8 -0.828505000 -1.897872000 -1.568661000
1 7.818230000 18.655118000 -1.885327000 8 1.439810000 -2.491024000 -1.421091000
93


6
6
6
6
6
6
6
6
6
6
6
6
6
1
1
1
1
6
1
1
1
1
6
6
6
6
6
6
1
1
1
1
1
1
1
-2.772334000 3.640975000 -0.082955000 8 5.419542000 0.809025000 1.750762000
-2.797784000 2.214302000 0.010941000 6 5.163519000 0.277557000 3.040109000
-3.925323000 1.558057000 0.505440000 1 4.145343000 0.510968000 3.379477000
-1.644466000 1.441455000 -0.400406000 1 5.310720000 -0.810517000 3.066502000
-1.684996000 0.022336000 -0.319236000 1 5.883265000 0.753691000 3.708575000
-2.830726000 -0.623799000 0.215686000 11 SCF E(RB3LYP) = -1383.27327750 au (not fully
-3.968487000 0.169090000 0.631123000 converged)
-1.666242000 4.302675000 -0.539196000 B3LYP/6-31G(d) opt
-0.505709000 2.189186000 -0.859233000 6 2.357400000 3.222642000 2.645247000
-2.940921000 -2.045049000 0.390687000 6 2.077940000 3.692021000 1.365152000
-5.124162000 -0.473296000 1.176891000 6 1.928769000 1.947031000 3.004474000
-5.174258000 -1.830896000 1.330107000 1 2.398774000 4.692074000 1.080623000
-4.060743000 -2.621409000 0.931230000 1 2.129558000 1.555114000 3.997844000
-2.128282000 -2.677098000 0.066806000 6 1.387171000 2.915824000 0.423814000
-5.963422000 0.151415000 1.473728000 6 1.241612000 1.163444000 2.079711000
-6.055513000 -2.308070000 1.750038000 1 0.930543000 0.167263000 2.372275000
-4.102832000 -3.701114000 1.049205000 6 0.955968000 1.618782000 0.782898000
-0.517293000 3.558640000 -0.924726000 1 2.894932000 3.848412000 3.352501000
-3.659690000 4.188464000 0.226183000 6 1.172982000 3.537586000 -0.945333000
-1.656869000 5.387181000 -0.603680000 6 0.181904000 0.675609000 -0.175304000
0.405009000 1.679286000 -1.148441000 8 -0.108673000 3.261372000 -1.491603000
0.367481000 4.083626000 -1.274710000 8 0.511486000 0.994279000 -1.559789000
2.872935000 -0.917845000 -0.319737000 6 -0.141597000 2.059148000 -2.209034000
3.612035000 -0.548443000 0.815607000 1 1.960966000 3.220839000 -1.647261000
3.178585000 -0.357056000 -1.559922000 1 -1.200191000 1.856653000 -2.394928000
4.644527000 0.386854000 0.708296000 1 0.404229000 2.141991000 -3.160695000
4.216905000 0.577429000 -1.658682000 6 2.872883000 -0.224555000 -1.196036000
4.946655000 0.954247000 -0.539657000 6 1.927736000 -1.161499000 -0.653178000
2.624101000 -0.667364000 -2.437573000 6 0.705324000 -0.796149000 -0.011110000
4.458926000 1.011850000 -2.625175000 6 2.300552000 -2.557392000 -0.743623000
5.756289000 1.674631000 -0.600651000 6 1.501842000 -3.526354000 -0.138507000
2.032252000 -2.687192000 0.550661000 6 0.405590000 -3.173916000 0.645021000
-4.788165000 2.145449000 0.813086000 6 0.010990000 -1.781841000 0.750387000
0.149694000 -0.127065000 -1.405144000 6 4.028786000 -0.629760000 -1.810591000
3.374333000 -1.001116000 1.773062000 6 3.493988000 -2.942870000 -1.432406000
94


Full Text

PAGE 1

MODELING OF LARGE SYSTEMS AND CHARGE TRANSFER REACTION MECHANISMS UTILIZING ELECTRONIC STRUCTURE THEORY by CARLY TAYLOR WOLFBRANDT B.S., University of Colorado Denver 2013 A thesis submitted to the Faculty of the Graduate School of the Unive rsity of Colorado in partial fulfillment of the requirements for the degree of Master of Science Chemistry Program 2017

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ii This thesis for the Mas ter of Science degree by Carly Taylor Wolfbrandt has been approved for the Chemistry Program by Haobin Wang Hai Lin Scott Reed May 13, 2017

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iii Wolfbrandt, Carly Taylor (M.S., Chemistry Program ) M odeling of Large Systems and Charge Transfer R eaction Mechanisms Utilizing Electronic Structure Theory Thesis directed by Professor Haobin Wang ABSTRACT Electronic struct ure theory calculations were used to investigate two systems: modeling of stable structures of RNA oligomers and photoinduced reaction mechanisms for photoremovable protecting groups (PPGs). For the first system, density functional theory (DFT) was perform ed on strands and duplexes of RNA oligomers of varying length, from 3 O 2 O3) and phosph ate phosphate distances, indicating a compacted structure consistent with experimental results. This structural information, along with experimental data, will be useful in designing stable compounds. The second study concerns the mechanism for deprotectio n of carbonyl groups from PPGs. The primary step of this reaction was found to be an ultrafast charge transfer reaction, which is followed by a dissociation reaction due to the transfer of energy to the reaction coordinate from the radiationless decay. Thi s mechanism provides insight into the viability of deprotection with multiple wavelengths, allowing for increased temporal and spatial control in photoinduced chemical reactions. The form and content of this abstract are approved. I recommend its publicati on Approved: Haobin Wang

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iv ACKNOWLEDGMENT S I would like to thank my advisor, Dr. Haobin Wang, for his patience, encouragement, and expert advice throughout my time in his group. I had a question about my research or w riting. This work would not have been possible without his tireless efforts, both in prioritizing my needs as a group member and as a student in the department. A special thanks to Dr. Hai Lin for making himself available to answer odd questions, provide insight, and making me feel as though I was an honorary member of his research group. The Lin lab supported me greatly, as colleagues and as friends, and were always I would also like to thank the groups of Drs. Scott Reed and Marino Resendiz for their br illiance in the laboratory. T heir experimental insights provide crucial context for this computational work. Furthermore, I must express my gratitude to my parents and partner for their support and motivation. Thank you for being understanding and providing me continuous encouragement, especially when things were particularly stressful. This absolutely would not be possible without you. Thank you. Finally, this project w ould have been impossible without support from the National Science Foundation (NSF) and the National Energy Research Scientific Computing Center (NERSC).

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v TABLE OF CONTENT S I. INTRODUCTION Computational Chemistry ................................ ................................ ................................ .... 1 Theory, Functionals and Computationa l Methods ................................ .............................. 1 Hartree Fock Theory ................................ ................................ ................................ ...... 1 Density Functional Theory ................................ ................................ ............................ 3 II. MOLECULAR MODELING OF OLIGONUCLEOTIDES OF RNA ................................ 6 Synthetically Modified Oligonucleotides of RNA ................................ ............................. 6 Introduction ................................ ................................ ................................ .................... 6 Investigated Systems ................................ ................................ ................................ ...... 7 Computational Methods ................................ ................................ ................................ 9 Model Systems and Nature of Stability in Modified RNA ................................ ............... 10 Trimer Model System Results ................................ ................................ ..................... 10 6mer Model System Results ................................ ................................ ........................ 12 Oligonucleotides of Interest for Further Study ................................ ............................ 15 Conclusion s ................................ ................................ ................................ ........................ 15 III. ELECTRON TRANSFER IN PHOTOCHEMICAL REACTIONS ................................ 17 Theoretical Background ................................ ................................ ................................ .... 17 Introduction ................................ ................................ ................................ .................. 17 Kinet ic Model of Electron Transfer ................................ ................................ ............. 17 Transition State Theory ................................ ................................ ................................ 18 Marcus Theory of Electron Transfer ................................ ................................ ............ 20 Generalized Mulliken Hush Method ................................ ................................ ........... 22

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vi IV. ELECTRON TRANSFER MECHANISM ................................ ................................ ........ 24 Photoremovable Protecting Groups ................................ ................................ ................... 24 Introduction ................................ ................................ ................................ .................. 24 Investigated Systems ................................ ................................ ................................ .... 25 Proposed Deprotection Mechanism ................................ ................................ ................... 26 Mechanism Overview ................................ ................................ ................................ .. 26 Franck Condon Excitation : 1 ................................ ................................ .................. 28 Radiationless Decay : 2 ................................ ................................ ............................ 30 Transition State Barrier : 3 ................................ ................................ ....................... 31 Generalized Mulliken Hush Coupling Results ................................ ............................ 32 Summary ................................ ................................ ................................ ...................... 33 PPGs of Interest for Further Study ................................ ................................ ..................... 33 Conclusions ................................ ................................ ................................ ........................ 35 IV. CONCLUSION ................................ ................................ ................................ .................. 36 Conclusions ................................ ................................ ................................ ........................ 36 REFERENCES ................................ ................................ ................................ ........................ 38 APPENDIX A. Additional Figures and Data for Chapter II ................................ ................................ 43 B. Additional Figures and Data for Chapter IV ................................ ............................... 45 C Cartesian Coordinates ( ) and Absolute Energies for the Optimized Structures ....... 47

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1 CHAPTER I INTRODUCTION Computational Chemistry Computational chemistry is a fast evolving di scipline, the primary concern of which is the modeling of chemical systems. The advent of massively parallel computing systems has allowed for computer simulations of larger and more complicated systems without having to rely solely on classic mechanical d escripti ons. Furthermore, the relative inexpensive nature of computation makes it a valuable tool when used in conjunction with experimental chemistry. For instance, predictions in chemical behavior can be made with computational methods and used to suppor t experimental findings. In this way, computational and experimental chemistry support and strengthen each other. Theory Functional s and Computational Methods Hartree Fock Theory The task of electronic structure theory is to solve the time independent, non relativistic Schrdinger equation for electrons (1 .1 ) which has the form of an eigenvalue equation for the total energy, E and the n electron wave function 1 The electronic Hamiltonian specifies the kinetic and potential energies for each electron ( 1. 2) The solution of the Schrdinger equation is based on t he Born Oppenheimer approximation which assumes the nuclei are stationary from the perspective of the electrons. This a llows separable treatment of the nuclear and electronic contributions 2 The nuclear repulsion term

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2 is treated as an external potential and is added total energy Hamiltonian The resulting electronic Hamiltonian is given by ( 1. 3 ) where the first two terms constitute the one electron Hamiltonian and the last term is the two electron interaction which is responsible for the electron correlation effect 3 The core of various approximate numerical methods is how to handl e electron correlations efficiently. To satisfy the Pauli exclusion principle, the set of single electron basis functions in the form of spin orbital functions, are combined in the form of a Slater determinant to ensure that the wave function remains anti symmetric In the simplest, one determinant form, the wave function is expressed as ( 1. 4 ) where each row or column represents an individual electron. 3 This ensures that when two electrons exchange, the wave function changes sign and thus remains anti symmetric. Neglecting electronic correlations, the iterative solution leads to the so called Hartree Fock (HF) approximation 3 An obvious drawback to t he HF method is that the many electron wave function is forced into the form of a Slater de terminant which only accounts for electron electron interactions in an average way 3 The difference bet ween the true energy and the HF energy, termed correlation energy, is completely ignored. There are various post self consistent field (SCF) methods that can include (approximately) the correlation energy, e.g., perturbation

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3 methods, configuration interact ion approaches, coupled cluster theory, and multiconfiguration methods. These approaches appear to be too expensive when the size of the molecular system becomes very large. A compromise is to use Density Functional Theory (DFT) which has built in correcti ons, though they are very often semi empirical Density Functional Theory In 1964 Hohenberg and Kohn proposed two formal theorems for obtaining the ground state energy based upon the electronic density, ( r ) 4 Their work was motivated by the Thomas Fermi model but utilized a more soli d theoretical foundation. 4 The Hamiltonian is expressed as a function of density ( 1. 5 ) In the case of a nondegenerate ground state the electronic density in the ground state is given by ( 1. 6 ) In 1965, Kohn and Sham built upon the aforementioned work an d proposed a set of self consistent equations which include approximations for electronic exchange and correlation. 5 These equations, known as the Kohn Sham equations invoke non interaction electronic interaction for a fictitious system 5 What makes modern DFT calculations feasible is owed largely to the Kohn Sham approximation, which has a computational scaling similar to HF but is capable of achieving high er accuracy. DFT was well known in solid accurate enough by chemists. The main contributor who led DFT to its practical regime is Axel Becke ; he introduced accurate approximations for the exchange correl ation functional that are beyond simple physical arguments. 6 An example is the hybrid functional which

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4 mixes pure DFT with HF cont ributions. This works surprisingly well in practice (despite functional and the correlation functional of Lee, Yang and Parr (B3LYP). 6 7 Today, the usage of B3LYP is nearly ubiquitous, despite there being hundreds of proposed functionals, each with their own pros and cons. The DFT theorem can also be applied to obtain excited state properties of a system, which is the main idea behind t ime dependent den sity functional theory (TDDFT ). This method was formally proposed in 1984 by Runge and Gross 8 The time dependent Schrdinger equation is given by ( 1. 7 ) where the Hamiltonian has the form ( 1. 8 ) dependent external potential. Their t heorem was employed in the formulation of TDDFT b y utilizing the change in external potential over time to generate the density. 9 In our work, a linear response approximation of the TDDFT was used to obtain the excited state properties of the system. To solve the Kohn Sham SCF equation, program packages such as Gaussian 09 use Gaussian basis sets to approximate the atomic orbitals 10 In principle, the larger the basis set, the more accurate the expected results. In this work we calibrate the calculations with different basis set functions. The systematic na ming scheme proposed by Pople was used; f or example, in the basis set 3 21G, each inner shell is represented by a contracted basis function from three primitive Gaussian functions, and the outer valence orbitals are described by two sets of contracted basi s functions with two and one primitive Gaussians, respectively. 11 The

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5 6 31G basis is a reasonably large basis set in this naming scheme Furthermore, the addition of an asterisk (*) at the end of the basis set add polarization functions ( d orbital for main group elements). 10 Diffuse functions may also be added (+) which are particularly useful in cases where electronic transfer is observed. In cases where van der Waals interactions (dispersion forces) become important empirical corrections are included via the D3 model of Grimme. 12 For the linear response TDDFT calculations, there is a fundamental defect for long range charge transfer excited states. This is partially compensated by either a long range corrected (L C) functional, or a similar scheme such as the Coulomb attenuating method (CAM B3LYP ) 12 For calculations in strong polar solvents, such as water, an impl icit solvation model is used to emulate the reaction environment. The Polarizable Continuum Model (PCM) emulates a solvent by treating the solution as a dielectric continuum 13 Embedding the solute in a cavity surrounded by continuous media, t he electron density is used to model the electrostatic potential of the solute and the solvent reaction field is made self consistent with this potential. 10, 14 16

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6 CHAPTER II MOLECULAR MODELING OF OLIGONUCLEOTIDES OF RNA Synthetically Modified Oligonucleotides of R NA Introduction Ribonucleic acid (RNA) is a biological macromolecule with essential uses in the human body. RNA in its natural form is primarily composed of the four nucleobases adenine (A), guanine (G), cytosine (C) and uracil (U), as shown in Figure 2 .1. 17 18 Adenine and guanine are heterocyclic bases belonging to the purine group, while cytosine and uracil belong to the pyrimidine group. Figure 2.1 Nucleobases of RNA When these nitrogenous bases combine with ribose and a phosphate group they form a nucleotide; nucleotides are monomer units, as shown in Figure 2.2, which polymerize to form oligonu cleotides (ONs) of RNA. 19

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7 Figure 2.2 Nucleotide of RNA with the nitrogenous base guanine The most common naturally occurring RNA ONs are formed with the bases from Figure 2.1. Synthetically modified RNA can be formed by altering the nucl eobase or adding functi onal groups to the ribose ring. One example is uridine modified at the C5 position (numbered positions shown in Figure 2.10) with the small functional group thiophene ; this modified nucleobase was found to be accommodated by T7 RNA p olymerase albeit in low yields 20 A nother common place to modify is the ribose ring a O position as shown in Figure s 2.2 and 2.3 19 Examples of modifications at this position with small functional groups have been discussed by Nakamura et al and indicate that the size of th iophene will allow for compatibility with biological processes. 21 24 Investigated Systems Thiophene functionalization carried out at the ribose ring results in varying numbers of modifications per strand, from si ngle to fully modified oligonucleotides. 25 Figure 2.3 indicates the position of the modification s

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8 Figure 2.3 Overvi ew of O 2 thiophenylmethyl functionalization Duplexes were formed from the modified and unmodified strands. Figure 2.4 shows the formation of a modified duplex, where each strand has four modifications and each duplex has eight. Unmodified (canonical) duplexes were also studied. 0 or 4 modifications per strand functionalization on ribose ring where B = A, G, C, U strand with 4 modifications 2 methylthiophene functional group

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9 Figure 2.4 Formation of a duplex from two strands functionalized with four O 2 thiophenylmethyl groups These complexes were compared with their canonical analogues using strands and duplexes in varying lengths, from 3 to 6 nitrogenous bases, referred to as trimers and "6mers" The sequences can be found in Fi gures 2.5 and 2.6 1 C G A 3 C G A 2 G C U 5' 4 G C U 5' Figure 2.5 Sequence of trimer oligonucleotides 1:2 (canonical) and 3:4 (modified) where the underlined nucleotides represent 2' O 2 thiophenylmethyl modified positions. 5 C G A G C U 7 C G A G C U 6 G C U C G A 5' 8 G C U C G A 5' Figure 2.6 Sequence of 6mer oligonucleotides 5:6 (canonical) and 7 :8 (modified) where the underlined nuc leotides represent 2' O 2 thiophenylmethyl modified positions. Computational Methods To shed light on the effect that a 2 methylthiophenyl group has on single and double strands of RNA we performed electronic structure calculations using DFT on modified c omplexes of RNA c O 2 thiophenylmethyl g roups 25 Calculations were performed using the quantum chemistry program Gauss ian 09. 10 T he B3LYP hybrid

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10 functional with both 3 21G* and 6 31G* basis sets were used in geometry optimizations, correction. 6, 13 14 Gas phase calculations were unable to model the RNA duplexes, therefore it was necessary to use PCM to emulate the reaction environment. Calculations with dispersion correctio ns more closely modeled the helical backbone and matched experimental data showing tightening of the helix. Model Systems and Nature of Stability in Modified RNA Trimer Model System Results Due to the size and complexity of the systems, initial geometry o ptimizations were performed on canonical and modified trimers The sequences of these molecules can be found in Figure 2.5 Optimizations using single strands supported that the duplex is the thermodynamically favored conformation. To bette r understand th e stabilities free energy calculations were performed on 1:2 and 3:4 at the 3 21G* level. Frequency calculations are expensive, therefore it was ideal to perform these calculations on a small trimer be seen in Figure s 2. 7 and 2.8

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11 Figure 2. 7 400 K at 10 K increments) where G = 15.8753 kcal mol 1 39.1042 kcal mol 1 77.4296 cal mol 1 K 1 0 5 10 15 20 25 30 0.0024 0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 1/T

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12 Figure 2.8 400 K at 10 K increments) 20.4236 kcal mol 1 44.8528 kcal mol 1 81.4308 cal mol 1 K 1 As due to the negative G values, we expect these two reactions to be spontaneous at low temperatures. The formation of the canonical trimer has slightly more free energy, the enthalpy is more negative and the magnitud e of the negative entropy change is larger. Therefore, we expect this reaction to be very slightly more favorable. However, due to the inherent error in these calculations, it should be noted that this evidence is inconclusive. 6mer Model System Results Du plexes 5:6 and 7:8 were optimized at both the 3 21G* and 6 31G* levels; their sequences can be found in Fig ure 2.6 and images in Figure 2.9 Optimizations using single strands supported that the duplex is the thermodynamically favored conformation. 0 5 10 15 20 25 30 35 40 0.0024 0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 1/T

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13 Since a free energy calculation was not feasible for a model system of this size, with 5:6 and 7:8 having over 450 atoms each, other methods to assess the stability had to be employed. A common method is the study of torsional angles and phosphate phosphate bond distances, with shorter bonds being indicative of a more compact and stable structure. Quantitative analysis was performed by measuring the torsion angles d osidic dihedral angle between sugar and nucleobase) and ribose ring). 25 Figure s 2.2 an d 2.10 define these values. Figure 2.9 Side by side comparison of the optimized structures of 5:6 (left) and 7:8 (right).

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14 Figure 2.10 Torsion angles and and phosphate with numbering ring for pyrimidine (left) and purine (right) 26 27 The covariance matrix for th ese angles can be seen i n Figure 2.11 The first thing to notice abo ut Figure 2.11 is that the angles obtained from our calculations are in the region corresponding to A form geometries, 25 Secondly, the modified 6mer can be found clustered in a region of lower values, which indicate stability since a smaller implies a tighter backbone angle, and therefore a tighter helix. Figure 2. 11 A plot di 65 70 75 80 85 90 95 100 -170 -165 -160 -155 -150 -145 -140 ( ) ) Canonical Modified group pyrimidine O 4 C 1 N 1 C 2 C 5 C 4 C 3 O 3 purine O 4 C 1 N 9 C 4 C 5 C 4 C 3 O 3

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15 Table 2.1 Phosphate phosphate bond distances from optimized 3 21G* 6mer Phosphate Phosphate Bond Distances Canonical Modified 5.9 0.4 5.5 0.3 The phosphate phosphate distances, from Figure 2.10 can be seen in Table 2.1 where shorter bond distances indicate stability of the 6mer. Oligonucleotides of Interest for Further Study To shed further light on the nature of stability induced by these modifications, calculations were performed on duplexes with v arying degrees of modification. Modified duplexes 9:6 10:6 11:6 7:6 are being optimized at the 6 31G* level. 9 C G A G C U 10 C G A G C U 11 C G A G C U Figure 2.12 Sequence of oligonucleotides with varying degrees of substitu tion where the O 2 thiophenylmethyl modified positions. Once the optimizations are complete, these strands and duplexes can be analyzed the same way as above; measuring the torsion angles d osidic dihedral angle b etween sugar and nucleobase) and angle along the ribose ring) and comparing them to assess stability induced or diminished by staggered functionalization. Conclusions Synthetically modified RNA can produce functional nucleotides with m any applications ranging from nanomaterials to gene therapy. 28 29 Thiophene was chosen as it allows the ability to expand the possible functionalizations of interest. Thiophene is also attractive due to the small size, which helps prevent structural disruptions to the b ackbone, and properties which allow for chemical reactions without disrupting the native biochemical processes of RNA. 25 A stabili zing effect was found when complementary nucleobases of

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16 O position. The covariance matrix for the dihedral angles obtained from our calculations are in the region corresponding to A form geometries. Moreover, the modifie d 6mer can be found clustered in a region of lower values, indicating increased stability. These results are in congruence with experimental findings, and further research is needed to investigate the destabilizing effect when modifications are intercal ated. 25 U sing computational methods, we can model very large oligonucleotide systems using an electronic theory approach. Traditionally, these types of molecules have been modeled using mixed quantum and classical mechanics, due to restrictions in computing power and time. 30 Recent advancements in computational power have enabled us to forgo classic mechanical approximations in favor of a full DFT investigation. The la rgest system investigated in this study (over 450 atoms) was optimized using both smaller and larger basis sets (3 21G* and 6 31G*) and support experimental findings. The error margin is still large for many quantitative results, but that does not diminish the importance of the qualitative findings.

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17 CHAPTER III ELECTRON TRANSFER IN PHOTOCHEMICAL REACTI ONS Theoretical Background Introduction transition state theory, Marcu r, and the Generalized Mulliken Hush method. These sections set the theoretical groundwork for the proposed electron transfer mechanism given in Chapter IV. Kinetic Model of Electron Transfer Engel and Reid have outlined a ki netic model of electron transfer reactions, where electron transfer reactions are defined as outer sphere redox reactions where an exchange of charge between a donor molecule (D) and an acceptor (A) molecule occurs. 31 These reactions are ubiquitous in chemistry and biology; the most prevalent is the photosynthetic reaction of CO 2 a nd H 2 O to form sugars and O 2 (3.1) In Reaction (3.1), the acceptor CO 2 is reduced while the donor H 2 O is oxidized. A generalized electron transfer reaction can be written as (3.2) A reaction mechanism can also be written to describe electron transfer in a bimolecular reaction. The first step of the reversible reaction is the formation of a donor acceptor complex (3.3)

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18 Next, electron transfer occurs between the donor and acceptor in the complex, leaving each species with a charge, or back electron transfer occurs in the complex, reforming the donor acceptor complex (3.4) The final step is the separation of the complex into isolated oxidized donor and reduced acceptor molecules (3.5) Transition State Theory eoretical model for reaction rates and barriers, known as Transition State Theory (TST). 32 Theoretically, reactions are thought to pass over an energy barrier, with reactants on one side and products on t he other. When the molecule is at the height of the barrier, it is said to be a transiti on state, as shown in Figure 3.1

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19 Figure 3.1 Adiabatic plot of Gibbs free energy versus the reaction coordinate for an exothermic reaction where is the Gibbs energy of activation We can use this theory to form the following equations: (3.6) (3.7) where the transition state, is equivalent to the complex from Reactio n (3.4). 31 As shown in Figure 3.1 the experimentally determined rate constan t will have a dependence on the Gibbs energy of activation. Transition state theory has several known limitations, namely the assumption that there exists an equilibrium between the donor acceptor complex and the transition state. 32 This implies that each transition state has time to equilibrate and reach a Boltzmann distribution. Furthermore, it relies on a classical mechanical description of the nuclei and neglects tunneling effects.

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20 Marcus Theory of E lectron Transfer Rudolph Marcus earned a Nobel prize for his work on re defining the relationship in Reaction (3.7) using a diabatic representation of electron transfer. 33 39 A graph illustrating the connection betw een Gibbs energy and the rate constant can be seen in Figure 3. 2 Figure 3.2 Diabatic plot of Gibbs free energy versus the reaction coordinate for the normal Marcus regime where is the reorganization energy Marcus made important determinations regarding the chemical factors that affect in particular the solute/solvent effects of electron transfer. He proposed that the solute and solvent with relax following electron tr ansfer; t he solute will relax to a new equilibrium geometry following electron transfer as the bonds reorder and nuclei relax, and the solvent will respond to the change in charge distribution following electron transfer. He related these relaxations, refe rred to as the reorganization energy, to the Gibbs energy of activation in the following manner (3.8 )

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21 Marcus theory proposes other regimes, where different values for are shown by different overlap in the parabolic potential energy surfaces, as sh own in Figures 3.2 and 3.3 As Equatio n (3. 8 ) shows, there is a minimum when It is predicted that the rate will increase with until a maximum rate occurs when then the rate will decrease. The inverted regime can be seen in Figure 3.3 Figure 3.3 Diabatic plot of Gibbs free energy versus the reaction coordinate for the inverted Marcus regime This inverted behavior indicates that extra energy is needed to reach the crossing point. Per the Franck Condon principle, this moti on of electron transfer can be expressed as a vertical transition due to the speed at which excitation occurs; the nuclear geometry is estimated to remain constant during this transition. During this fast electron transfer process, the nuclei have no time to change positions and the electron transfer can occur at the reactant

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22 and product intersection. Theoretically, this location has the highest probability due to the wave function overlap between the reactant and products. Generalized Mulliken Hush Method Robert Cave and Marshall Newton utilized Marcus theory in their development of the Generalized Mulliken Hush (GMH) theory. 40 41 GMH predicts that, in electron transfer re actions, charges are localized on donor and acceptor centers. This allows for the construction of diabatic states from adiabatic states. Figure 3.4 Diabatic (left) and adiabatic (right) plots where H DA is the matrix coupling element These diabatic sta tes can be constructed from the Hamiltonian and dipole operator eigenstate matrices given by (3.9 ) (3.10 ) w here is the ground state dipole, is the excited state dipole and is the transition dipole. A unitary transformation of yields

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23 (3.11 ) which can be used to transform the eigenstate Hamiltonian to the charge localized states (3.12 ) where (3.13 ) A graphical representation of the above values is given in Figure 3. 5 Figure 3.5 Potential ene rgy diagram for constructing diabatic states from an adiabatic representation by the GMH method The weak coupling limit is given by (3.14 ) where the Marcus electron transfer rate, is defined by the electronic coupling, the reorganization energy, and the standard Gibbs free energy,

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24 CHAPTER IV ELECTRON TRANSFER REACTION ME CHANISM P hotoremovable Protecting Gro u ps Introductio n Photoremovable protecting groups (PPGs) provide a means of exciting one group o f molecules with light while leaving another inactive, resulting in a controlled release of various chemicals. 42 Neurotransmitters, pheromones, fragrances, acids, bases, and oxidants can all be re leased by PPGs. 43 There have been many developments in applications of PPGs with particular emphasis on the release of organic molecules. 42, 44 The importance of cyclic acetals as carbonyl PPGs lies in their stability and lack of reactivity. 45 46 Two representations of one protecting group molecule can be seen in Figure 4.1. Figure 4 .1 Two representations of a model PPG where the substitutions on the left molecule are R 1 = H and R 2 = (CH 2 ) 2 Ph. Cyclic acetals are for med by the reaction of a carbonyl with two alcohol equivalents and the removal of water, which is an important feature since acetal formation is reversible in acidic environments. Once a carbonyl is converted to an acetal, it is unreactive in neutral or ba sic environments and can be exposed to strongly nucleophilic compounds without concern.

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25 Investigated Systems Photoexcitation reactions of the PPGs for carbonyl compounds, shown in Figure 4. 2 were chosen based on multi disciplinary relevance as well as the availability of experimental and simulation data suggesting a plausible mechanistic pathway. 47 Figure 4 .2 Model PPGs 1 6 It was suggested that 1 and 2 should be the most likely to dissociate, due to the excited state meta effect. PPGs driven by the meta effect are s aid to dissociate more readily due to the donation of electron density in C 1 facilitating the benzylic C O dissociation. 47 50 Furthermore, it has been shown by Zimmerman and co workers that meta d irecting groups stabilize cations, lending heterolysis of the C O bond to be energetically favored over homolysis. 48 50 The expected zwitterionic transition state and products in this reaction can be seen in Figure 4.3 1. R 1 = H R 2 = H 3. R 1 = H R 2 = H 5. R 1 = H R 2 = H 2. R 1 = H R 2 = (CH 2 ) 2 Ph 4. R 1 = H R 2 = (CH 2 ) 2 Ph 6. R 1 = H R 2 = (CH 2 ) 2 Ph 1

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26 Figure 4.3 Proposed transiti on state (R 1 /R 2 = H) and products 7 and 8 where 8 is the protected carbonyl of interest The lack of possibility for free radicals, along with the presence of structural features which help delocalize charge, enhance the attractiveness of the syst em for computational study. 43 In order to fully understand a theoretically proposed mechanism, one must first underst and the theory behind the calculations. Chapter III discuss es the theoretical background for the proposed deprotection mechanism; in particular, the kinetic model of electron transfer, transition state theo ry, Marcus theory an d the Generalized Mulliken Hush method are discussed in detail Proposed Deprotection Mechanism Mechanism Overview Deprotection is proposed to occur as follows (representations can be found in Figures 4.4 and 4.5) : (blue, 1) the molecule experiences Franck Condon excitation upon irradiation, ( red, 2) reorganization energy is small and there is not a large change in the excited state geometry, so the molecule quickly undergoes radiationless decay ( purple, 3) the molecule maintains sufficient energy to overco me the transition state barrier ( blue, 4) the molecule dissociates. A representation of the molecules at each point can be seen in Figure 4.4 + 7 8

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27 Figure 4.4 Franck Condon energy level diagram shown with molecular representations of the reaction. As shown i n Figure 4.5, photoexcitation at point A leads to a vertical transition to point B. Relaxation occurs rapidly from point B to point C, where internal conversion allows for radiationless decay to point D. The molecule still possesses sufficient energy at po int D to overcome the boundary and dissociate.

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28 Figure 4.5 Franck Condon energy level diagram with naming conventions for excitation, de excitation and the energy at the transition state. The next sections will go through the calculated transitions s tep by step. Franck Condon Excitation : E 1 Before absorption occurred, each molecule occupied the lowest vibrational state of its lowest electronic state after optimization using DFT at the 6 31G* level and the B3LYP hybrid functional. 51 Linear approximation TDDFT calculations at the 6 31G* level indicated the most likely excited states for each molecule Excitation energies can be found in Table 4.1.

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29 Table 4.1 Excita tion energies E 1, for molecules 1 6 using TDDFT at the 6 31G* level and B3LYP hybrid functional molecule E 1 (eV) 1 6.0867 2 6.2727 3 6.6734 4 6.6484 5 6.8559 6 6.6757 Per the Franck Condon principle, this motion is expressed as a vertical transition due to the speed at which excitation occurs; the nuclear geometry is estimated to remain constant during this transition. 51 This vertical excitation passes through many vibrational levels in the upper electronic state, therefore there are many accessible vibrational states for the molecules to now occupy. Theoretically, the molecules have the highest probability of occupying the upper vibrational state that has the most overlap with the ground state wave function. 51 A fundamental assumption of the Franck Condon principle is the separation of the electronic and vibrational wave functions, known as th e Born Oppenheimer approximation. There was no indication that dissociation occurred after excitation TDDFT single point energy calculations at the 6 31G* level showed no dissociation, and optimizations allowed for vibrational relaxation to the lowest vi brational state of the highest excited electronic state also did not dissociate Since the molecule has so much excess energy at this point, a remaining option for the molecules is to undergo internal conversion and transition to the ground electronic stat e.

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30 Radiationless Decay : E 2 The molecules transitioned to the ground electronic state through internal conversion, also described as radiationless decay since there is no emission of a photon in this process. De excitation energies can be found in Table 4.2. Table 4.2 De excitat ion energies E 2, for molecule s 1, 3 6 using TDDFT at the 6 31G* level and B3LYP hybrid functional molecule E 2 (eV) 1 3.8114 3 4.3044 4 3.6428 5 4.7201 6 5.3076 The remaining energy is then transferred to the vibrational modes of the molecule. T his remaining energy, which is the difference in the excitation and de excitation energies ( E 1 E 2 ), can be seen in Table 4.3. Table 4.3 Energy remaining ( E 1 E 2 ) for molecules 1, 3 6 after radiationless decay for each molecule molecule Remaining Ene rgy (eV) 1 2.2753 3 2.3690 4 3.0056 5 2.1358 6 1.3681

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31 Transition State Barrier: E 3 Transition states were found using Gaussian 09 by requesting a minimization to a transition state rather than a local minimum. The transition state is defined as a first order saddle point on the potential energy surface where, like minima, the forces are all zero; unlike minima, at a saddle point one of the second derivatives is negative. The transition state was found by manually building a guess structure and foll owing the eigenvector corresponding with this negative eigenvalue to the saddle point. 10 If a true transition state is reached, there will be only one imaginary frequency which arises from the reaction coordinate. Although this is a costly calculation, calculating t he Hessian at each step ensures that the correct eigenvector is followed to the true transition state structure. The energy of the molecule at the transition state can then be compared to the energy at the optimized ground state to obtain the energy heigh t of the barrier. Table 4.4 Transition state energy barrier E 3, for each molecule using DFT at the 6 31G* level and B3LYP hybrid functional molecule E 3 1 1.8336 2 1.5456 3 1.8128 4 1.6573 5 1.8479 6 1.6944 As can be seen by comparing Figures 4 .3 and 4.4, the energy remaining after radiationless decay exceeds the energy required to overcome the transition state barrier. If the

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32 excess energy is released as heat, the molecules would never show any indications of dissociation. These molecules were found to dissociate readily upon irradiation per experimental data, so the excess energy must be transferred to the reaction coordinate to overcome the transition state barrier. Generalized Mulliken Hush Coupling Results The Generalized Mulliken Hush (GMH ) method, a useful scheme discussed in detail in Chapter III, was used to calculate diabatic electron transfer coupling Since TDDFT with commonly used functionals is usually not correct for charge transfer problems, we performed calculations with LRC dens ity functionals, which yields better coupling results for charge transfer states. 52 53 The calculations were performed at the 6 31G* level in Q Chem 4.4 developer version and results are shown in Table 4 5 54 Table 4. 5 Coupling results for charge transfer states using GMH method at the transition state molecule coupling (eV) 1 1.1823 2 0.2378 3 1.3625 5 1.3687 4 1.3932 6 1.3607 Radiationless decay can be described as a transition between two differ ent diabatic states, where excess energy is released through the vibrational modes. When coupling is large (greater than 1 eV), the reaction can be assume to proceed at the sub picosecond timescale. On average, fluorescence takes nanoseconds which cannot c ompete in these types

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33 of ultrafast reactions Since the coupling was calculated to be strong, the competition between radiationless and radiational decay can be ignored. Summary Molecules 1 6 are proposed to dissociate in the following manner an ultraf ast charge transfer reaction where the primary driving force for dissociation is the transfer of energy to the reaction coordinate following radiationless decay. There are no indications that these molecules will fluoresce, since the coupling is so large. The molecules possess sufficient energy following radiationless decay in order to overcome the transition state barrier. There are no indications that molecules 1 and 2 will dissociate more readily than molecules 3 6 However, it is worth noting that converged higher excited states o f molecule 2 were unable to be reached. Furthermore, its coupling constant is lower than the others by a n order of magnitude. A more in depth study of this molecule might prove interesting; there is a possibility for a competing mechanism for dissociat ion, such as steric hindrance from the larger R group. P PGs of Interest for Further Study P hotochemical reactions involving PPGs have been used extensively in organic synthesis, however, the selectivity of specific protecting groups to different wavelength combinations has not been widely studied. 43, 47 Our research, in collaboration with Dr. Scott indicated that multiple wavelength photo deprotection is possible Two molecules, shown in Figure 4.6 were studied computationally with differe nt R groups to assess whether multiple wavelength deprotection was possible. The R groups chosen were anthracene and anisole, due to differences in their max

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34 While initial studies are inconclusive as to the viability of deprotection with multiple wav elengths, there is indication that the R 1 and R 2 positions do not act independently. As shown in Table 4.7 TDDFT studies performed at the 6 31G* level indicate that the max is nearly the same independent of substitution site. Table 4 6 max for molecu les 9 12 shown in Figure 4.5 with varying substitutions molecule wavelength (nm) 9 241.52 10 237.92 11 240.75 12 236.92 Using information about PPGs 1 6 we have proposed a mechanism for the dual deprotection of molecule 12 in Scheme 4 .1. 43, 47 9 R 1 = anthracene, R 2 = anisole, R 3 = H, R 4 = H 11. R 1 = anthracene, R 2 = anisole, R 3 = H, R 4 = H 10 R 1 = anthracene, R 2 = H, R 3 = anisole, R 4 = H 12 R 1 = anthracene, R 2 = H, R 3 = anisole, R 4 = H Figure 4.6 Four multiple wavelength PPGs with varying substitution sites

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35 Scheme 4.1 Pro posed dual wavelength deprotection m echanism of 10 in acidic c onditions Conclusions Electronic structure theory calculations were conducted to shed light on the mechanism of dissociation in protecting group reactions. The reaction was found to be an ultrafast charge transfer reaction wh ere the primary driving force for dissociation is the transfer of energy to the reaction coordinate following radiationless decay. There are no indications that molecules 1 6 will fluoresce, since the coupling is so large. The molecules must possess suffic ient energy following radiationless decay in order to overcome the transition state barrier. There are no indications that molecules 1 and 2 will dissociate more readily than molecules 3 6 However, it is worth noting that converged higher excited states o f molecule 2 were unable to be reached. Furthermore, its coupling constant is lower than the others by a full order of magnitude. A more in depth study of this molecule might prove interesting; there is a possibility for a competing mechanism for dissociat ion, such as steric hindrance from the larger R group. Further research is needed to establish whether or not dual wavelength deprotection is possible.

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36 CHAPTER V CONCLUSION Conclusions Synthetically modified RNA can produce functional nucleotides with ma ny applications ranging from nanomaterials to gene therapy. 28 29 Thiophene was chosen as it allows the ability to expand the possible functionalizations of interest. Thiophene is also attractive due to the small size, which helps prevent structural disruptions to the ba ckbone, and properties which allow for chemical reactions without disrupting the native biochemical processes of RNA. 25 A stabiliz ing effect was found when complementary nucleobases of O position. The covariance matrix for the dihedral angles obtained from our calculations are in the region corresponding to A form geometries. Moreover, the modified 6mer can be found clustered in a region of lower values, indicating increased stability. These results are in congruence with experimental findings, and further research is needed to investigate the destabilizing effect when modifications are intercala ted. 25 Photo induced chemical reactions are of fundamental importance in chemistry, biochemistry and materials science. A comprehensive understanding of such reaction mechanisms is crucial for designing novel electronic and optical materials, next generation solar cells, and alternative synthetic methods. 47 Deprotection of the carbonyl from PPGs 1 6 was found to be an ultrafast charge transfer re action where the primary driving force for dissociation is the transfer of energy to the reaction coordinate following radiationless decay. There are no indications that molecules 1 and 2 will dissociate more readily than molecules 3 6 A more in depth stu dy of molecule 2 might prove interesting for a possible competing

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37 mechanism. Further research is needed to establish whether or not dual wavelength deprotection is possible. From organic synthesis to quantum calculations, the ability to predict chemical ch anges is constantly evolving as technology advances. As computers become more and more advanced, they allow for quantum chemical calculations on increasingly larger systems. The large systems of interest herein (some greater than 450 atoms) take advantage of the recent strides in computational science. Computational studies are especially effective when used in conjunction with synthetic chemistry, either concurrently with experimental analysis or predictively. The latter case is particularly useful, as rel iable computational studies can facilitate synthetic endeavors.

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38 REFERENCES 1. Schrdinger, E., Ann. Phys. 1926, 384 (4), 361 376. 2. Born, M.; Oppenheimer, J. R., Ann. Phys. 1927, 20 (389), 457 484. 3. Engel, T.; Reid, P., Hartree Fock. In Physical Chemistry Prentice Hall: 2010. 4. Hohenberg, P.; Kohn, W., Phys. Rev. 1964, 136 (3B). 5. Kohn, W.; Sham, L. J., Phys. Rev. 1965, 140 (4), 1133. 6. Becke, A. D., Phys. Rev. A 1988, 38 3098. 7. Lee, C.; Yang, W.; Parr, R. G., Phys. Rev. B. Condens. Matter 1988, 37 (2), 785 789. 8. Runge, E.; Gross, E. K. U., Phys. Rev. Lett. 1984, (52), 997. 9. Gross, E. K. U.; Kohn, W., Advances in Quantum Chemistry 1990, 21 255 291. 10. M. J. Frisch, G. W. T., H. B. Schlegel, G. E. Scuseria, ; M. A. R obb, J. R. C., G. Scalmani, V. Barone, B. Mennucci, ; G. A. Petersson, H. N., M. Caricato, X. Li, H. P. Hratchian, ; A. F. Izmaylov, J. B., G. Zheng, J. L. Sonnenberg, M. Hada, ; M. Ehara, K. T., R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, ; Y. Honda, O. K., H. Nakai, T. Vreven, J. A. Montgomery, Jr., ; J. E. Peralta, F. O., M. Bearpark, J. J. Heyd, E. Brothers, ; K. N. Kudin, V. N. S., T. Keith, R. Kobayashi, J. Normand, ; K. Raghavachari, A. R., J. C. Burant, S. S. Iyengar, J. Tomasi, ; M. Cossi, N. R ., J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, ; V. Bakken, C. A., J. Jaramillo, R. Gomperts, R. E. Stratmann, ; O. Yazyev, A. J. A., R. Cammi, C. Pomelli, J. W. Ochterski, ; R. L. Martin, K. M., V. G. Zakrzewski, G. A. Voth, ; P. Salvador, J. J. D., S. Dapprich, A. D. Daniels, ; O. Farkas, J. B. F., J. V. Ortiz, J. Cioslowski, ; and D. J. Fox, Gaussian 09, Revision D. 01. 2013. 11. Ditchfield, R.; Hehre, W. J.; Pople, J. A., J. Chem. Phys. 1971, 54 724. 12. Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H., J. Chem. Phys. 2010, 132 154104.

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40 27. Neurotiker, Skeletal formula (showing numbering convention for substituent groups) of purine, a simple aromatic ring. 2008 28. Seeman, N C., Annu. Rev. Biochem. 2010, 79 65 87. 29. Terrazas, M.; Ivani, I.; Villegas, N.; Paris, C.; Salvans, C.; Brun Heath, I.; Orozco, M., Nucleic Acids Res. 2016, 44 (9), 4354 4357. 30. Accts. of Chem Res. 2010, 43 (1), 40. 31. Engel, T.; Reid, P., Electron Transfer. In Physical Chemistry 2 ed.; Prentice Hall: 2010. 32. Eyring, E., Chemistry: Foundations and Applications. Ed. J. J. Lagowski. Vol. 4. New York: Macmillan Reference USA, 2004. p64 68 33 Marcus, R. A., Discuss Faraday Soc. 1960, 21 34. Marcus, R. A., J. Chem. Phys. 1956, (24), 966. 35. R. A. Marcus, J. C. P., 679 (1965), J. Chem. Phys. 1965, 43 679. 36. Marcus, R. A., Rev. Mod. Phys. 1993, 65 599. 37. Marcus, R. A.; Sutin, N., Biochi mica et Biophysica Acta 1985, (811), 265 322. 38. Silverstein, T. P., J. Chem. Educ. 2012, 89 (9), 1159 1167. 39. Georgievskii, Y.; Hsu, C. P.; Marcus, R. A., J. Chem. Phys. 1999, (110), 5307. 40. Cave, R. J.; Newton, M. D., J. Chem. Phys. 1997, 106 (22) 41. Cave, R. J.; Newton, M. D., Chem. Phys. Lett. 1995, 249 (1 2), 15 19.

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41 42. Zhao, H.; Sterner, E. S.; Coughlin, E. B.; Theato, P., Macromolecules 2012, (45), 1723. 43. Kostikov, A.; Wirz, J., Chem. Rev. 2013, 113 119 191. 44. Warther, D.; Gug, S.; Specht, A.; Bolze, F.; Nicoud, J. F.; Mourot, A.; Goeldner, M., Bioorg. Med. Chem. 2010, 18 45. Sloof, G., Recueil des Travaux Chimiques des Pays Bas 1938, 57 (6), 673 676. 46. Wuts, P.; Greene, T., Chapter 4. Protection for the Carbonyl Group In Protective Groups in Organic Synthesis Online, 2006. 47. Yang, H.; Zhang, X.; Zhou, L.; Wang, P., J. Org. Chem. 2007, 7 (76), 2040 2048. 48. Zimmerman, H. E. S., V. R. J. Am. Che m. Soc. 1963, 85 (915). 49. Zimmerman, H. E., J. Am. Chem. Soc. 1995, 1117 8988. 50. Zimmerman, H. E., J. Phys. Chem. A 1998, (102), 5616. 51. Atkins, P., Physical Chemistry 6 ed.; Oxford University Press: 1998. 52. Z. Q. You; Hung, Y.; C. P. Hsu, J. Ph ys. Chem. B. 2015, 119 7480 7490. 53. Yanai, T.; Tew, D. P.; Handy, N. C., Chem. Phys. Lett. 2004, (393), 51 57. 54. Y. Shao, Z. G., E. Epifanovsky, A. T. B. Gilbert, M. Wormit, J. Kussmann, A. W. Lange, A. Behn, J. Deng, X. Feng, D. Ghosh, M. Goldey P. R. Horn, L. D. Jacobson, I. Kaliman, R. Z. Khaliullin, T. Ks, A. Landau, J. Liu, E. I. Proynov, Y. M. Rhee, R. M. Richard, M. A. Rohrdanz, R. P. Steele, E. J. Sundstrom, H. L. Woodcock III, P. M. Zimmerman, D. Zuev, B. Albrecht, E. Alguire, B. Austin, G. J. O. Beran, Y. A. Bernard, E. Berquist, K. Brandhorst, K. B. Bravaya, S. T. Brown, D. Casanova, C. M. Chang, Y. Chen, S. H. Chien, K. D. Closser, D. L. Crittenden, M. Diedenhofen, R. A. DiStasio Jr., H. Dop, A. D. Dutoi, R. G. Edgar, S. Fatehi, L. Fusti M olnar, A. Ghysels, A. Golubeva Zadorozhnaya, J. Gomes, M. W. D. Hanson Heine, P. H. P. Harbach, A. W. Hauser, E. G. Hohenstein, Z. C. Holden, T. C. Jagau, H. Ji, B.

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42 Kaduk, K. Khistyaev, J. Kim, J. Kim, R. A. King, P. Klunzinger, D. Kosenkov, T. Kowalczyk, C. M. Krauter, K. U. Lao, A. Laurent, K. V. Lawler, S. V. Levchenko, C. Y. Lin, F. Liu, E. Livshits, R. C. Lochan, A. Luenser, P. Manohar, S. F. Manzer, S. P. Mao, N. Mardirossian, A. V. Marenich, S. A. Maurer, N. J. Mayhall, C. M. Oana, R. Olivares Amaya, Pieniazek, A. Prociuk, D. R. Rehn, E. Rosta, N. J. Russ, N. Sergueev, S. M. Sharada, S. Sharmaa, D. W. Small, A. Sodt, T. Stein, D. Stck, Y. C. Su, A. J. W. Thom, T. Tsuchimochi, L. Vogt, O Vydrov, T. Wang, M. A. Watson, J. Wenzel, A. White, C. F. Williams, V. Vanovschi, S. Yeganeh, S. R. Yost, Z. Q. You, I. Y. Zhang, X. Zhang, Y. Zhou, B. R. Brooks, G. K. L. Chan, D. M. Chipman, C. J. Cramer, W. A. Goddard III, M. S. Gordon, W. J. Hehre, A Klamt, H. F. Schaefer III, M. W. Schmidt, C. D. Sherrill, D. G. Truhlar, A. Warshel, X. Xua, A. Aspuru Guzik, R. Baer, A. T. Bell, N. A. Besley, J. D. Chai, A. Dreuw, B. D. Dunietz, T. R. Furlani, S. R. Gwaltney, C. P. Hsu, Y. Jung, J. Kong, D. S. Lambre cht, W. Liang, C. Ochsenfeld, V. A. Rassolov, L. V. Slipchenko, J. E. Subotnik, T. Van Voorhis, J. M. Herbert, A. I. Krylov, P. M. W. Gill, and M. Head Gordon. Advances in molecular quantum chemistry contained in the Q Chem 4 program package. [Mol. Phys. 1 13, 184 215 (2015)].

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43 APPENDIX A ADDITIONAL FIGURES A ND DATA FOR CHAPTER II Figure A.2 400 K at 5 K increments ) where G = 27.0113 kcal mol 1 44.1013 kcal mol 1 56.9666 cal mol 1 K 1 0 5 10 15 20 25 30 35 40 45 50 0.0024 0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 1/T Figure A.1 Side by side comparison of the optimized structures canonical (left) and modified (right) dimers. Dashed lines within the helix represent hydrogen bonds between the strands.

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44 Figur e A.3 400 K at 5 K increments) where G = 24.2594 kcal mol 1 39.3520 kcal mol 1 50.3086 cal mol 1 K 1 0 5 10 15 20 25 30 35 40 45 50 0.0024 0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 1/T

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45 APPENDIX B ADDITIONAL FIGURES A ND DATA FOR CHAPTER IV Table B.1 Coupling results for charge transfer states using GMH method at the ground state molecule excitation energy (eV) oscillator strength coupling (eV) 2 4.8723 0.067760 2.426818 1 4.8408 0.064740 2.393382 3 4.7949 0.067444 2.383986 5 5.1553 0.033592 2.179227 4 4.7709 0.064236 2.36 7367 6 5.1356 0.034174 2.112277 Table B.2 Coupling results for charge transfer states using GMH method at the excited state molecule excitation energy (eV) oscillator strength coupling (eV) 2 4.6379 0.066374 2.295142 1 3.9875 0.080361 1.734402 3 4 .3947 0.076263 2.194795 5 4.7954 0.048902 2.071878 4 4.3813 0.073712 2.182455 6 4.7717 0.049159 2.010648

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46 Table B.4 Transition state to excited state gap for each molecule using TDDFT at the 6 31G* level and B3LYP hybrid functional molecule E 4 1 3.2085 2 1.9435 3 3.2447 5 3.4276 4 3.3028 6 3.4795

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47 APPENDIX C CARTESIAN COORDINATES ( ) FOR THE OPTIMIZED STRUCTURES IN CHAPTER S II and IV CHAPTER II 1 SCF E(RB3LYP) = 3854.60801632 au B3LYP/3 21G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosy mm scf=xqc 1 1.965512000 6.578618000 5.437784000 8 2.755617000 6.195621000 4.973736000 6 5.081890000 5.101738000 2.228680000 6 6.067536000 4.689484000 3.324417000 6 5.422535000 5.310548000 4.580770000 6 4.918127000 6.652370000 4.038148000 6 3.762186000 7.246665000 4.813187000 8 4.478864000 6.359201000 2.649361000 1 5.571123000 5.199769000 1.261878000 1 6.205630000 3.613499000 3.361526000 8 7.334065000 5.391089000 3.109684000 1 7.553420000 5.734174000 4.028244000 1 4.616740000 4.710401000 4.998020000 1 5.754699000 7.356350000 4.014741000 1 4.150732000 7.581819000 5.783316000 1 3.367578000 8.110498000 4.265118000 8 6.443664000 5.589246000 5.588859000 7 4.025519000 4.065361000 2.122543000 6 4.386056000 2.870230000 1.406833000 8 5.527100000 2.830317000 0.893972000 7 3.461382000 1.869320000 1.356767000 6 2.299136000 1.978426000 2.012637000 7 1.495777000 0.889910000 2.037663000 6 1.911767000 3.182788000 2.691466000 6 2.814605000 4.199362000 2.736803000 1 1.938079000 0.025023000 1.857118000 1 0.592177000 0.929775000 2.496422000 1 0.962727000 3.259321000 3.201189000 1 2.654033000 5.103446000 3.312397000 8 7.323678000 3.225082000 5.559071000 6 8.490975000 0.010105000 3.829601000 6 8.986705000 0.372677000 5.227928000 6 8.899176000 0.964328000 5.981506000 6 9.312453000 1.977162000 4.910406000 6 8.729273000 3.355194000 5.121282000 8 8.804659000 1.420139000 3.632927000 1 8.956747000 0.615875000 3.067370000 1 8.432386000 1.199024000 5.667856000 8 10.414851000 0.701483000 5.124376000 1 10.819929000 0.158522000 5.866842000 1 7.906722000 1.179886000 6.367974000 1 10.404229000 2.031946000 4.872136000 1 9.283217000 3.870186000 5.909225000 1 8.746660000 3.924899000 4.190009000 8 9.898646000 1.015853000 7.049870000 7 4.761820000 2.809615000 1.853263000 6 6.10399900 0 3.109004000 1.987609000 7 6.549308000 4.285189000 1.505207000 7 6.958406000 2.270224000 2.574164000 6 6.379235000 1.143750000 3.041474000 6 5.034619000 0.757411000 2.967823000 6 4.119290000 1.612684000 2.293991000 8 2.898433000 1.487052000 2.038241000 7 4.866275000 0.482170000 3.616596000 6 6.072463000 0.836557000 4.034932000 7 7.033761000 0.12593000 0 3.698552000

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48 1 4.136141000 3.462573000 1.384035000 1 5.947543000 4.963550000 1.055094000 1 7.534044000 4.500550000 1.608743000 1 6.341774000 1.728290000 4.578168000 15 6.748929 000 4.327986000 6.661223000 8 7.866169000 4.814447000 7.529092000 8 5.441146000 3.787290000 7.142621000 8 8.829735000 0.908876000 8.263834000 6 7.002874000 3.857640000 7.05420800 0 6 7.024503000 4.337050000 8.511591000 6 8.109156000 3.449730000 9.164024000 6 9.121732000 3.270182000 8.023687000 6 9.853841000 1.947801000 8.069789000 8 8.324021000 3.302749 000 6.771404000 1 6.774675000 4.694789000 6.392583000 1 6.038673000 4.256861000 8.981195000 8 7.554081000 5.689374000 8.505652000 1 8.187385000 5.675134000 9.291180000 1 7.7326 50000 2.482952000 9.494594000 1 9.819711000 4.111272000 8.038225000 1 10.562082000 1.924776000 8.902244000 1 10.366971000 1.786608000 7.118763000 8 8.798184000 4.198121000 10.217577 000 1 8.311668000 4.060552000 11.074579000 7 2.454675000 2.825345000 4.862218000 6 3.078978000 3.995690000 5.114928000 7 4.275549000 4.175247000 5.719277000 6 4.807338000 3.0124 81000 6.143181000 6 4.249159000 1.734381000 5.981549000 6 3.049392000 1.658990000 5.245007000 7 2.501252000 0.477797000 4.869380000 7 5.087411000 0.763144000 6.554984000 6 6.12 4766000 1.438910000 7.038431000 7 6.006952000 2.817606000 6.806186000 1 2.570750000 4.891942000 4.779906000 1 3.176923000 0.281064000 4.692598000 1 1.776158000 0.552175000 4.1595 82000 1 6.991189000 1.030149000 7.534659000 15 9.295793000 0.651795000 8.571468000 8 10.468029000 0.658740000 9.498232000 8 8.013691000 1.398748000 8.767971000 2 SCF E(RB3LYP) = 3802.4224 7134 au B3LYP/3 21G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc 8 5.038238000 7.812039000 2.966820000 6 6.366780000 4.984918000 1.308008000 6 7.375854000 4.870280000 2.459284000 6 7.325969 000 6.263626000 3.123592000 6 7.063721000 7.199750000 1.932293000 6 6.211290000 8.392899000 2.307326000 8 6.298490000 6.395795000 0.945650000 1 6.713688000 4.387556000 0.46364600 0 1 7.130502000 4.044131000 3.134533000 8 8.692108000 4.751340000 1.856698000 1 9.243957000 5.379080000 2.422331000 1 6.529114000 6.354580000 3.859958000 1 8.020949000 7.501948 000 1.500252000 1 6.749079000 9.053956000 2.993641000 1 5.899931000 8.928691000 1.407786000 8 8.648580000 6.616747000 3.645636000 1 8.721298000 6.280437000 4.579133000 7 3.1996 46000 1.194051000 0.371966000 6 4.499082000 1.391842000 0.048730000 7 5.055040000 0.473121000 0.864314000 7 5.208632000 2.456700000 0.323368000 6 4.537766000 3.296891000 1.142934 000 6 3.231333000 3.182776000 1.624451000 6 2.429498000 2.092268000 1.182778000 8 1.213027000 1.860058000 1.350483000 7 2.918945000 4.291296000 2.427215000

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49 6 4.005669000 5.0508 29000 2.432767000 7 5.034207000 4.481975000 1.649029000 1 2.666609000 0.407249000 0.006355000 1 4.563907000 0.352935000 1.181859000 1 6.007812000 0.623652000 1.174050000 1 4.11 5645000 5.998404000 2.928560000 8 0.072826000 7.431587000 1.820294000 6 2.609446000 7.777050000 0.837842000 6 3.522713000 8.094484000 0.349544000 6 2.541452000 8.391232000 1.5049 69000 6 1.369592000 9.083013000 0.804791000 6 0.017216000 8.851828000 1.460989000 8 1.353170000 8.503676000 0.569645000 1 3.053638000 8.101149000 1.775523000 1 4.240603000 7.30 2939000 0.557683000 8 4.204521000 9.362452000 0.050565000 1 4.063935000 9.888929000 0.896689000 1 2.222590000 7.507396000 2.051166000 1 1.578377000 10.152926000 0.730588000 1 0. 041074000 9.475003000 2.359456000 1 0.777419000 9.097057000 0.755968000 8 3.137932000 9.374121000 2.418500000 7 2.318402000 6.344561000 0.971162000 6 2.912306000 5.629180000 2.07 2342000 8 3.752865000 6.215125000 2.781579000 7 2.516955000 4.321924000 2.251448000 6 1.651206000 3.744598000 1.401935000 7 1.282370000 2.463941000 1.620827000 6 1.056701000 4. 450780000 0.312335000 6 1.406552000 5.746069000 0.144280000 1 1.500278000 1.998926000 2.496550000 1 0.705306000 1.988689000 0.933604000 1 0.336557000 4.013141000 0.356084000 1 0.938481000 6.350629000 0.619448000 15 3.904447000 8.707586000 3.755333000 8 4.543495000 9.843645000 4.484817000 8 2.993333000 7.678385000 4.353041000 1 5.277087000 4.455450000 1. 045654000 8 4.490439000 5.024966000 1.252430000 6 1.840093000 6.999544000 2.902240000 6 1.251526000 7.310930000 1.515217000 6 2.373735000 6.809023000 0.594327000 6 3.629003000 7.254804000 1.343609000 6 4.858764000 6.427569000 1.040600000 8 3.281990000 7.066421000 2.782250000 1 1.467647000 7.711570000 3.637263000 1 0.313527000 6.791709000 1.350274000 8 1.101005000 8.749174000 1.408511000 1 0.103247000 8.870363000 1.289221000 1 2.339517000 5.721916000 0.534314000 1 3.803204000 8.314827000 1.140952000 1 5.137129000 6.620979000 0.003278000 1 5.681161000 6.735089000 1.697525000 8 2.383744000 7.386754000 0.734625000 7 1.444559000 5.629294000 3.336124000 6 0.100137000 5.508515000 3.702056000 8 0.669106000 6.486308000 3.675014000 7 0.283343000 4.229541000 4.047853000 6 0.508133000 3.058403000 4.017462000 8 0.014966000 1.951408000 4.260243000 6 1.880694000 3.307342000 3.633160000 1 2.549271000 2.463599000 3.569836000 6 2.293539000 4.550724000 3.282716000 1 1.300107000 4.098565000 4.075203000 1 3.275052000 4.758679000 2.870822000 15 1.524864000 6.623830000 1.931707000 8 2.195593000 6.954594000 3.227802000 8 1.221380000 5.216295000 1.498450000 1:2 SCF E(RB3LYP) = 7657.37918362

PAGE 56

50 B3LYP/3 21G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc 1 1.982674000 6 .320589000 5.443355000 8 2.814324000 5.990842000 5.010559000 6 5.234344000 5.108063000 2.285451000 6 6.225927000 4.735871000 3.385540000 6 5.546935000 5.307773000 4.644236000 6 4.956994000 6.622146000 4.119071000 6 3.745336000 7.116240000 4.878046000 8 4.562876000 6.323167000 2.712322000 1 5.737477000 5.252391000 1.330309000 1 6.419840000 3.672174000 3 .398467000 8 7.454606000 5.504461000 3.165383000 1 7.683855000 5.846443000 4.079314000 1 4.776296000 4.651958000 5.042763000 1 5.737306000 7.387025000 4.117066000 1 4.085977000 7.468163000 5.858809000 1 3.294534000 7.952590000 4.332687000 8 6.542828000 5.640745000 5.670182000 7 4.215882000 4.032362000 2.110507000 6 4.593144000 2.903069000 1.355659000 8 5.816042000 2.778862000 1.044348000 7 3.630044000 2.014018000 0.999941000 6 2.355346000 2.140547000 1.448988000 7 1.445579000 1.275074000 1.000381000 6 2.014008000 3.194799000 2.360296000 6 2.959124000 4.129093000 2.645775000 1 1.719386000 0.525513000 0.335407000 1 0.489027000 1.316312000 1.337227000 1 1.023306000 3.258436000 2.782867000 1 2.786097000 4.953628000 3.327447000 8 4.703066000 7.593166000 3.027470000 6 6.545556000 4.933455000 0.907379000 6 7.483915000 4.772205000 2.109798000 6 7.086676000 5.958360000 3.015312000 6 6.817939000 7.053476000 1.979605000 6 5.938130000 8.178489000 2.448995000 8 6.154443000 6.344471000 0.853388000 1 7.028996000 4.627290000 0.019369000 1 7.376957000 3.790854000 2.578885000 8 8.840739000 5.042770000 1.654739000 1 9.215671000 5.592321000 2.412589000 1 6.196324000 5.759579000 3.609578000 1 7.779920000 7.450217000 1.643868000 1 6.457935000 8.755470000 3.216429000 1 5.678138000 8.816148000 1.602755000 8 8.233972000 6.405042000 3.801864000 1 8.297644000 5.830796000 4.612357000 7 4.442941000 0.366690000 0.150899000 6 5.750460000 0.768513000 0.040158000 7 6.615743000 0.148764000 0.498864000 7 6.169838000 2.021149000 0.226168000 6 5.198857000 2.813533000 0.724165000 6 3.870810000 2.475156000 1.010220000 6 3.418906000 1.169751000 0.673882000 8 2.242044000 0.711392000 0.782843000 7 3.198289000 3.580709000 1.563316000 6 4.094837000 4.560824000 1.591926000 7 5.32824400 0 4.140729000 1.076065000 1 4.143249000 0.583978000 0.228485000 1 6.338825000 1.128904000 0.694679000 1 7.556505000 0.159448000 0.719381000 1 3.968443000 5.554841000 1.982606000 8 7.526490000 3.329611000 5.568546000 6 8.520234000 0.075531000 3.835595000 6 9.076604000 0.302900000 5.207363000 6 9.001344000 1.037281000 5.934911000 6 9.450277000 2.02958900 0 4.861646000 6 8.921641000 3.427849000 5.088521000 8 8.901160000 1.468511000 3.595611000

PAGE 57

51 1 8.898701000 0.573208000 3.045176000 1 8.528389000 1.116785000 5.671147000 8 10.497720 000 0.650296000 5.063085000 1 10.951384000 0.127863000 5.785066000 1 7.992351000 1.268624000 6.258878000 1 10.541192000 2.048117000 4.800865000 1 9.515940000 3.919394000 5.86049100 0 1 8.924126000 4.007223000 4.164747000 8 9.933195000 1.106496000 7.060341000 7 4.393579000 2.636639000 2.483383000 6 5.688212000 3.078420000 2.653717000 7 5.942152000 4.370545 000 2.374085000 7 6.682499000 2.275653000 3.076245000 6 6.269445000 1.028219000 3.376629000 6 4.968964000 0.519647000 3.296112000 6 3.949112000 1.340000000 2.763339000 8 2.7498 14000 0.999674000 2.534789000 7 4.937355000 0.815276000 3.727392000 6 6.192126000 1.108696000 4.040522000 7 7.049435000 0.017050000 3.829530000 1 3.637057000 3.315886000 2.155150 000 1 5.171154000 5.057143000 2.271976000 1 6.880032000 4.706707000 2.567292000 1 6.557917000 2.025695000 4.465384000 15 6.957693000 4.384221000 6.694582000 8 8.081389000 4.8986 02000 7.543431000 8 5.701720000 3.777198000 7.241445000 8 0.386337000 7.930871000 1.836759000 6 2.416967000 7.926801000 0.748505000 6 3.344728000 8.216847000 0.425639000 6 2.36 1196000 8.567624000 1.562256000 6 1.280097000 9.375682000 0.830791000 6 0.116786000 9.318177000 1.419044000 8 1.233493000 8.753462000 0.530866000 1 2.877722000 8.152972000 1.7051 57000 1 4.016132000 7.387817000 0.628708000 8 4.098223000 9.440174000 0.123189000 1 4.031833000 9.972100000 0.970891000 1 1.938473000 7.693910000 2.051665000 1 1.603212000 10.41 2683000 0.725240000 1 0.170909000 9.985725000 2.282158000 1 0.835984000 9.608701000 0.652513000 8 3.020083000 9.434141000 2.542059000 7 2.027549000 6.498100000 0.757195000 6 2. 785798000 5.629391000 1.562296000 8 3.785641000 6.104158000 2.185635000 7 2.425389000 4.326061000 1.617089000 6 1.355834000 3.848732000 0.927569000 7 1.059474000 2.560807000 1.06 4179000 6 0.598392000 4.722047000 0.086194000 6 0.973475000 6.021587000 0.018756000 1 1.664413000 1.947891000 1.651342000 1 0.364606000 2.129440000 0.464882000 1 0.254456000 4. 396722000 0.486220000 1 0.450902000 6.719008000 0.619053000 15 3.695319000 8.616806000 3.836524000 8 4.489814000 9.642406000 4.587141000 8 2.643551000 7.747976000 4.458162000 8 8.733967000 0.720474000 8.318672000 6 7.237903000 3.836132000 6.728505000 6 7.187692000 4.419229000 8.147976000 6 8.070995000 3.442599000 8.958304000 6 9.163362000 3.080229000 7. 945634000 6 9.804046000 1.731097000 8.148206000 8 8.488653000 3.094807000 6.619728000 1 7.181320000 4.626439000 5.979916000 1 6.161427000 4.501074000 8.515995000 8 7.894180000 5.690530000 8.132149000 1 8.436609000 5.640301000 8.982337000 1 7.529727000 2.558324000 9.288939000

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52 1 9.928837000 3.860222000 7.966949000 1 10.434854000 1.748789000 9.040091000 1 10.400867000 1.492926000 7.267033000 8 8.737825000 4.156627000 10.047419000 1 8.114183000 4.190727000 10.822717000 7 2.472121000 3.462042000 4.896510000 6 3.346277000 4.494179000 4.888835000 7 4.597067000 4.479227000 5.378132000 6 4.928861000 3.278730000 5.907515000 6 4.117338000 2.138050000 5.964935000 6 2.819375000 2.245285000 5.417005000 7 1.929423000 1.250135000 5.369651000 7 4.813239000 1.078977000 6.567769000 6 6.009530000 1.578981000 6.878425000 7 6.124639000 2.916921000 6.493791000 1 2.986899000 5.399564000 4.422742000 1 2.212913000 0.317569000 5.653368000 1 1.063058000 1.374850000 4.816001000 1 6.825793000 1.065790000 7.359882000 15 9.212610000 0.845174000 8.536520000 8 10.310093000 0.918500000 9.553855000 8 7.946679000 1.652168000 8.612267000 1 5.618454000 5.041473000 1.064877000 8 4.751549000 5.513044000 1.179137000 6 1.828639000 7.052740000 2.967171000 6 1.329965000 7.542339000 1.602557000 6 2.538401000 7.221451000 0.709580000 6 3.708472000 7.635458000 1.602238000 6 5.018579000 6.952173000 1.281550000 8 3.272885000 7.220012000 2.971687000 1 1.360591000 7.613773000 3.774563000 1 0.438672000 7.002798000 1.316170000 8 1.112468000 8.974947000 1.656000000 1 0.141797000 9.082939000 1.388407000 1 2.581730000 6.156516000 0.498385000 1 3.816210000 8.722646000 1.568236000 1 5.383449000 7.357817000 0.330402000 1 5.746590000 7.173084000 2.069771000 8 2.587996000 7.974614000 0.536733000 7 1.499594000 5.610052000 3.156083000 6 0.191943000 5.319648000 3.568127000 8 0.672036000 6.220808000 3.680499000 7 0.052713000 3.997416000 3.828745000 6 0.813438000 2.932125000 3.613805000 8 0.446484000 1.750011000 3.870933000 6 2.106430000 3.305697000 3.094105000 1 2.823713000 2.529225000 2.880911000 6 2.411533000 4.614150000 2.903553000 1 1.029277000 3.764871000 4.216241000 1 3.366137000 4.939960000 2.505525000 15 1.915348000 7.300569000 1.885469000 8 2.664934000 7.848820000 3.062909000 8 1.728908000 5.820962000 1.669015000 3 SCF E(RB3LYP) = 4442.83103616 au B3LYP/3 21G* opt EmpiricalDispersion=GD3 scrf(pcm) nosymm scf=xqc 1 8.671959000 19.165602000 23.862360000 8 9.217177000 19.262937000 23.038195000 6 10.151216000 18.797714000 19.444666000 6 11.406329000 19.606343000 19.793143000 6 11.039642000 20.247796000 21.151253000 6 9.534518000 20.500221000 21.006553000 6 8.784640000 20.467848000 22.323316000 8 9.028986000 19.411176000 20.141738000 1 9.998119000 18.786936000 18.366997000 1 12.306134000 18.993504000 19.793960000 8 11.522961000 20.705955000 18.828048000 1 11.646575000 21.508009000 19.424217000 1 11.257369000 19.614548000 22.009052000 1 9.387535000 21.464423000 20.511181000

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53 1 9.042437000 21.375634000 22.882792000 1 7.707143000 20.458634000 22.122814000 8 11.679068000 21.563315000 21.277390000 7 10.273677000 17.394257000 19.896082000 6 10.903617000 16.485247000 18.981874000 8 11.359576000 16.950866000 17.913971000 7 10.956956000 15.166166000 19.348401000 6 10.493753000 14.777597000 20.540740000 7 10.574180000 13.462079000 20.852904000 6 9.924482000 15.687948000 21.488416000 6 9.828928000 16.992166000 21.124020000 1 11.039056000 12.834799000 20.205982000 1 10.3823090 00 13.148119000 21.798383000 1 9.680550000 15.358576000 22.485316000 1 9.441862000 17.761402000 21.783789000 8 13.907114000 20.417148000 21.261245000 6 15.200693000 17.228487000 20.090029000 6 16.580084000 17.698638000 20.605928000 6 16.382902000 19.221507000 20.715770000 6 15.405365000 19.583129000 19.592761000 6 14.493734000 20.733319000 19.954964000 8 14.603571000 18.3479700 00 19.357646000 1 15.326183000 16.362312000 19.437385000 1 16.848179000 17.229563000 21.548328000 8 17.660891000 17.284795000 19.720095000 1 15.902753000 19.452542000 21.668403000 1 15.95066 3000 19.836108000 18.682303000 1 15.079633000 21.653596000 20.034190000 1 13.700650000 20.842599000 19.210908000 8 17.589763000 20.011817000 20.553580000 7 13.214729000 13.231807000 22.4939000 00 6 14.222368000 13.275356000 21.549242000 7 14.785878000 12.115411000 21.158379000 7 14.647156000 14.423478000 21.018082000 6 14.027512000 15.513468000 21.517816000 6 13.002919000 15.56869 2000 22.465194000 6 12.471844000 14.355442000 22.977535000 8 11.482503000 14.153177000 23.719221000 7 12.658689000 16.910603000 22.713839000 6 13.450448000 17.635780000 21.939014000 7 14.294 225000 16.822986000 21.167767000 1 12.900929000 12.335430000 22.862505000 1 14.504965000 11.213010000 21.520763000 1 15.531652000 12.155194000 20.473514000 1 13.503545000 18.708958000 21.87076 4000 15 13.120816000 21.573561000 22.141538000 8 13.747664000 22.908454000 21.900291000 8 12.875235000 20.943494000 23.474553000 8 18.620801000 19.138113000 22.664393000 6 18.372964000 15.655 426000 23.973409000 6 19.519144000 16.057564000 24.910920000 6 20.062396000 17.355569000 24.271884000 6 19.877590000 17.088910000 22.771352000 6 19.641580000 18.337876000 21.957417000 8 18.6 69683000 16.231371000 22.665561000 1 18.298354000 14.567882000 23.923759000 1 19.177883000 16.175170000 25.944634000 8 20.563108000 15.059922000 24.755909000 1 21.396985000 15.627090000 24.718 769000 1 19.514195000 18.248072000 24.569906000 1 20.748997000 16.539452000 22.404896000 1 20.565098000 18.918114000 21.876945000 1 19.263945000 18.064102000 20.970878000 8 21.505906000 17.4 56262000 24.499523000 1 21.659037000 17.933820000 25.358768000 7 13.806355000 14.351904000 25.948535000 6 14.966857000 13.669659000 25.858096000 7 16.140653000 14.111092000 25.353414000 6 16 .073234000 15.401320000 24.972964000 6 14.946305000 16.236959000 25.045893000

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54 6 13.752693000 15.641027000 25.504134000 7 12.550382000 16.269299000 25.466402000 7 15.254886000 17.509937000 24.5 33886000 6 16.527817000 17.435833000 24.156613000 7 17.072820000 16.166365000 24.400710000 1 14.951156000 12.646868000 26.215123000 1 12.456510000 16.975764000 24.721396000 1 11.757231000 15 .627504000 25.508299000 1 17.117121000 18.210197000 23.687661000 15 18.227857000 20.598943000 21.977928000 8 19.473579000 21.336448000 21.602669000 8 17.123104000 21.149542000 22.826887000 6 17.704708000 17.898036000 18.380457000 1 18.031073000 18.936910000 18.465652000 1 16.710075000 17.860189000 17.917279000 6 19.294496000 17.324888000 16.410171000 6 18.680520000 17.066016000 17 .606374000 16 19.122319000 15.499106000 18.233630000 6 20.138079000 15.192280000 16.856016000 6 20.134730000 16.242333000 15.975340000 1 19.157372000 18.243893000 15.856579000 1 20.692411000 14.269572000 16.775807000 1 20.706208000 16.258721000 15.057696000 4 SCF E(RB3LYP) = 4390.64826456 au B3LYP/3 21G* opt EmpiricalDispersion=GD3 scrf(pcm) nosymm scf=xqc 8 12.833002000 5.527183000 19.417543000 6 14. 015235000 8.939075000 18.713907000 6 13.669101000 8.618832000 17.251884000 6 13.533465000 7.080078000 17.246461000 6 14.587314000 6.649136000 18.276037000 6 14.233757000 5.373946000 19.00 7579000 8 14.618119000 7.742547000 19.277739000 1 14.704358000 9.784088000 18.745913000 1 12.771273000 9.149768000 16.918935000 8 14.848206000 8.926691000 16.460903000 1 14.898158000 8. 136130000 15.835600000 1 12.548152000 6.733933000 17.554146000 1 15.558145000 6.573082000 17.779434000 1 14.353259000 4.520404000 18.330602000 1 14.865939000 5.274835000 19.889924000 8 1 3.968685000 6.544798000 15.954280000 1 13.184987000 6.518411000 15.341746000 7 11.710540000 12.912314000 20.743632000 6 12.857380000 12.843666000 19.974035000 7 13.514064000 13.990082000 19. 704024000 7 13.319126000 11.688826000 19.500668000 6 12.569952000 10.617873000 19.848741000 6 11.398926000 10.585338000 20.608097000 6 10.900634000 11.806962000 21.138184000 8 9.904833000 1 2.039284000 21.864663000 7 10.967071000 9.259519000 20.762613000 6 11.846846000 8.512331000 20.106334000 7 12.850281000 9.311617000 19.514616000 1 11.391791000 13.809724000 21.105811000 1 13.213519000 14.893226000 20.048535000 1 14.356600000 13.937007000 19.143947000 1 11.852117000 7.435297000 20.056585000 8 12.239741000 4.871892000 25.111512000 6 14.495381000 7.428304000 2 3.583578000 6 14.288409000 6.759862000 22.218584000 6 13.513934000 5.496884000 22.634269000 6 14.289484000 5.039404000 23.869507000 6 13.526301000 4.211101000 24.891187000 8 14.646308000 6.328669000 24.526024000 1 15.365051000 8.068605000 23.655835000 1 13.768771000 7.388533000 21.500863000 8 15.581198000 6.339108000 21.672166000 1 12.505129000 5.793950000 22.915676000 1 15.203722000 4.527701000 23.561588000

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55 1 13.379703000 3.196869000 24.507111000 1 14.111108000 4.189748000 25.816028000 8 13.437503000 4.451761000 21.638067000 7 13.303163000 8.242118000 23.906628000 6 13.265804000 9.568510000 23.371388000 8 14.316902000 10.010347000 22.824625000 7 12.108446000 10.261468000 23.512202000 6 11.042077000 9.722369000 24.135906000 7 9.889776000 10.419087000 24.106082000 6 11.112517000 8.446672000 24.783798000 6 12.252931000 7.733232000 24.611937000 1 9.051587000 10.023515000 24.517935000 1 10.300366000 7.988078000 25.327139000 1 12.344365000 6.720085000 24.968238000 15 12.155688000 4.569936000 20.579921000 8 11.899052000 3.192040000 20.054331000 8 11.088643000 5.438713000 21.190676000 1 10.179432000 8.483570000 29.768216000 8 11.004262000 8.152203000 29.325385000 6 14.541651000 7.701409000 28.235419000 6 14.082861000 6.508704000 27.406042000 6 12.643719000 6.316242000 27.896283000 6 12.795871000 6.563631000 29.403127000 6 11.533204000 7.025330000 30.095714000 8 13.822934000 7.642196000 29.496347000 1 15.618922000 7.701463000 28.395573000 1 14.207231000 6.659760000 26.341204000 8 14.835314000 5.320037000 27.838488000 1 14.117736000 4.622418000 27.912783000 1 11.928285000 7.005137000 27.454680000 1 13.180363000 5.657062000 29.877227000 1 10.833307000 6.179823000 30.106691000 1 11.768142000 7.311125000 31.127892000 8 12.243665000 4.925144000 27.675450000 7 14.168405000 8.971327000 27.527198000 6 14.948500000 9.310778000 26.414359000 8 15.8765050 00 8.583610000 26.017787000 7 14.584249000 10.494928000 25.801139000 6 13.549069000 11.389043000 26.184702000 8 13.369435000 12.445182000 25.558399000 6 12.787692000 10.906718000 27.316942000 1 11.943042000 11.492601000 27.643372000 6 13.100914000 9.742741000 27.930252000 1 15.010439000 10.666038000 24.886839000 1 12.496512000 9.320453000 28.723533000 15 11.210976000 4.6381500 00 26.386500000 8 10.808608000 3.204278000 26.493206000 8 10.256975000 5.794134000 26.293696000 6 16.452381000 7.515205000 21.413624000 1 15.865896000 8.440378000 21.440922000 1 16.86375 3000 7.385993000 20.411375000 6 18.354755000 8.558259000 22.844206000 6 17.514225000 7.540147000 22.475027000 16 17.803897000 6.099201000 23.410730000 6 19.080528000 6.877702000 24.2941090 00 6 19.259336000 8.176958000 23.893285000 1 18.330239000 9.541476000 22.394077000 1 19.614054000 6.351511000 25.071032000 1 19.992082000 8.843656000 24.326588000 1 9.799885000 11.14717 4000 23.379711000 3:4 SCF E(RB3LYP) = 8833.66515618 au B3LYP/3 21G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc 1 8.327112000 20.906510000 23.653007000 8 8.856566000 20.562346000 22.886526000 6 9.6956080 00 18.674442000 19.768271000 6 11.082847000 19.305200000 19.841918000 6 10.890428000 20.388064000 20.923380000 6 9.483037000 20.903346000 20.596611000 6 8.751735000 21.509681000 21.774096000

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56 8 8.736975000 19.707039000 20.123015000 1 9.495371000 18.270311000 18.776712000 1 11.842906000 18.561227000 20.042019000 8 11.332549000 20.010542000 18.582110000 1 11.682081000 20.8997320 00 18.893891000 1 10.959833000 20.008199000 21.940687000 1 9.555648000 21.630163000 19.783232000 1 9.238791000 22.463113000 22.013853000 1 7.708628000 21.696548000 21.493702000 8 11.82565 2000 21.491921000 20.709474000 7 9.578988000 17.561448000 20.754646000 6 10.125338000 16.309895000 20.383102000 8 10.837929000 16.263966000 19.340569000 7 9.830303000 15.231870000 21.1547670 00 6 9.156853000 15.361416000 22.322144000 7 8.852017000 14.256180000 23.000767000 6 8.751968000 16.660954000 22.781245000 6 8.949642000 17.724653000 21.960155000 1 9.129886000 13.32103 7000 22.631352000 1 8.375201000 14.320294000 23.893544000 1 8.265366000 16.781703000 23.737343000 1 8.666431000 18.736935000 22.228262000 8 14.331572000 4.966727000 19.559477000 6 14.414 103000 9.163814000 19.804822000 6 14.561488000 8.993719000 18.276656000 6 14.769802000 7.462319000 18.108858000 6 15.538287000 7.113167000 19.377362000 6 15.619183000 5.641528000 19.71776 1000 8 14.811023000 7.885854000 20.410191000 1 15.049588000 9.983433000 20.146167000 1 13.691428000 9.387736000 17.744037000 8 15.802377000 9.637940000 17.869421000 1 16.221734000 8.942 425000 17.270454000 1 13.836795000 6.899672000 18.068489000 1 16.546961000 7.509248000 19.281055000 1 16.301516000 5.202111000 18.982749000 1 16.025674000 5.501601000 20.721445000 8 15.6 76138000 7.195080000 16.992220000 1 15.141601000 7.113548000 16.157389000 7 11.008303000 12.838997000 20.498513000 6 12.159857000 12.851669000 19.735127000 7 12.479979000 14.006971000 19.125 994000 7 12.942691000 11.768609000 19.582371000 6 12.458937000 10.673975000 20.206134000 6 11.266895000 10.545783000 20.928061000 6 10.497596000 11.713773000 21.165762000 8 9.475452000 11.8 21184000 21.909690000 7 11.110363000 9.223475000 21.376607000 6 12.188997000 8.571097000 20.958472000 7 13.049709000 9.426669000 20.242649000 1 10.532192000 13.770104000 20.724056000 1 11 .893626000 14.860443000 19.199006000 1 13.381689000 14.046895000 18.666042000 1 12.393239000 7.510117000 21.070545000 8 13.831352000 19.972776000 20.748158000 6 15.442515000 16.696806000 19.7 26723000 6 16.740502000 17.297187000 20.282550000 6 16.366587000 18.785103000 20.388530000 6 15.460628000 19.043114000 19.179895000 6 14.406129000 20.105560000 19.398326000 8 14.814227000 17 .726869000 18.900893000 1 15.654982000 15.804480000 19.134359000 1 17.023838000 16.849386000 21.226983000 8 17.891465000 17.006016000 19.438447000 1 15.772974000 18.936490000 21.291566000 1 16.055008000 19.333596000 18.312215000 1 14.864103000 21.094556000 19.320752000 1 13.604827000 19.987507000 18.665381000 8 17.495564000 19.696267000 20.374865000 7 13.802155000 12.818599000 22 .549917000

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57 6 14.935825000 12.912974000 21.775228000 7 15.747098000 11.831541000 21.731065000 7 15.260646000 14.023507000 21.097385000 6 14.413131000 15.046365000 21.329265000 6 13.274852000 15.065797000 22.141755000 6 12.870787000 13.854448000 22.760229000 8 11.825265000 13.643589000 23.435585000 7 12.707594000 16.350195000 22.148109000 6 13.474180000 17.077428000 21.347307000 7 14.520419000 16.314966000 20.800551000 1 13.604665000 11.907211000 23.070274000 1 15.684373000 11.106632000 22.472383000 1 16.634752000 11.963651000 21.257519000 1 13.404518000 18.132463000 21.146343000 15 13.298062000 21.344259000 21.514934000 8 14.110670000 22.520286000 21.075516000 8 13.021855000 20.951103000 22.930023000 8 12.103685000 4.981024000 24.752968000 6 15.113970000 7.295747000 24.378389000 6 15.378494000 6.619547000 23.032477000 6 14.319423000 5.506274000 23.078488000 6 14.509811000 4.950428000 24.494896000 6 13.319071000 4.252322000 25.128736000 8 14.760713000 6.206783000 25.283399000 1 15.946661000 7.861443000 24.785846000 1 15.266705000 7.294625000 22.187146000 8 16.663838000 5.910599000 23.030364000 1 13.329771000 5.943681000 22.988733000 1 15.406761000 4.331264000 24.534387000 1 13.273468000 3.221548000 24.763984000 1 13.431598000 4.277240000 26.215852000 8 14.465904000 4.494632000 22.058813000 7 13.974942000 8.239403000 24.240028000 6 14.285179000 9.563839000 23.898919000 8 15.497936000 9.846898000 23.623908000 7 13.284741000 10.470066000 23.855521000 6 11.999942000 10.134140000 24.144668000 7 11.090755000 11.103641000 24.132052000 6 11.670627000 8.778141000 24.454117000 6 12.673672000 7.869823000 24.478297000 1 11.370355000 12.084113000 23.905340000 1 10.104733000 10.877774000 24.056123000 1 10.672165000 8.434217000 24.669150000 1 12.477088000 6.825889000 24.669879000 15 13.358811000 4.532717000 20.811721000 8 12.890866000 3.132819000 20.559675000 8 12.36677200 0 5.635307000 21.101706000 8 18.495450000 18.675600000 22.452224000 6 18.586228000 14.984899000 23.253156000 6 19.704272000 15.317031000 24.251468000 6 20.083256000 16.766216000 23.870652000 6 19.939409000 16.740578000 22.344420000 6 19.638588000 18.081312000 21.726824000 8 18.804060000 15.819214000 22.079077000 1 18.600115000 13.923638000 23.000755000 1 19.375274000 15.19345700 0 25.288437000 8 20.850118000 14.494949000 23.906363000 1 21.616779000 15.142997000 24.003705000 1 19.423879000 17.517969000 24.304186000 1 20.854915000 16.318737000 21.920437000 1 20.510397 000 18.735301000 21.818304000 1 19.360806000 17.939977000 20.682505000 8 21.501158000 17.001278000 24.146439000 1 21.594022000 17.320639000 25.084127000 7 14.505044000 13.036725000 25.64811800 0 6 15.657866000 12.453185000 25.243825000 7 16.671521000 13.061125000 24.604127000 6 16.435374000 14.377172000 24.404131000 6 15.288041000 15.091150000 24.775102000 6 14.260549000 14.359677 000 25.410933000

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58 7 13.084291000 14.875768000 25.780454000 7 15.407877000 16.436839000 24.401201000 6 16.602495000 16.532809000 23.822246000 7 17.266949000 15.297589000 23.799702000 1 15.7317 69000 11.395407000 25.446246000 1 12.848404000 15.813020000 25.471296000 1 12.335547000 14.236558000 26.103876000 1 17.060582000 17.416368000 23.403310000 15 18.003534000 20.164567000 21.894114 000 8 19.198347000 21.038766000 21.679257000 8 16.812010000 20.529962000 22.726800000 1 8.583471000 7.500096000 29.715411000 8 9.487395000 7.465859000 29.306122000 6 13.096688000 8.1238 33000 28.619323000 6 13.043146000 7.047336000 27.532672000 6 11.650588000 6.449646000 27.779543000 6 11.621075000 6.376690000 29.305654000 6 10.233597000 6.356263000 29.905949000 8 12.30 4218000 7.635221000 29.734220000 1 14.125649000 8.325080000 28.915626000 1 13.140896000 7.505074000 26.558935000 8 14.066807000 6.056411000 27.784705000 1 14.603311000 6.053282000 26.9287 22000 1 10.879746000 7.128274000 27.419929000 1 12.206829000 5.511447000 29.627402000 1 9.781084000 5.387403000 29.659064000 1 10.304009000 6.455252000 30.995758000 8 11.446948000 5.12 7879000 27.217168000 7 12.502464000 9.396019000 28.111352000 6 13.323781000 10.167218000 27.269825000 8 14.439071000 9.747748000 26.887091000 7 12.803472000 11.386631000 26.923209000 6 11. 534440000 11.876076000 27.222718000 8 11.186502000 13.025685000 26.842758000 6 10.712606000 10.965161000 27.988565000 1 9.702298000 11.258186000 28.226317000 6 11.220032000 9.784021000 28.42 1385000 1 13.451561000 12.030537000 26.353429000 1 10.638650000 9.064059000 28.988934000 15 10.746184000 5.030262000 25.716769000 8 10.019039000 3.724935000 25.652784000 8 10.104770000 6. 352077000 25.391349000 6 17.939704000 17.608050000 18.096811000 1 18.170428000 18.673635000 18.178838000 1 16.976087000 17.476205000 17.588655000 6 19.675150000 17.155533000 16.216551000 6 1 9.023391000 16.857948000 17.383251000 16 19.560535000 15.339294000 18.054692000 6 20.668438000 15.105455000 16.735157000 6 20.624418000 16.143009000 15.840785000 1 19.490960000 18.054141000 15. 643409000 1 21.300886000 14.231564000 16.695965000 1 21.239749000 16.198238000 14.953467000 6 17.853267000 6.791634000 23.066534000 1 18.675660000 6.112697000 23.303413000 1 17.762513000 7.518461000 23.880832000 6 17.545931000 8.732478000 21.413161000 6 18.106704000 7.537694000 21.791108000 16 19.149619000 6.906912000 20.537133000 6 18.828856000 8.274547000 19.517800000 6 17.954938000 9.155661000 20.106113000 1 16.841766000 9.245222000 22.052104000 1 19.270260000 8.344983000 18.535272000 1 17.534217000 9.997621000 19.577098000 5 B3LYP/6 3 1G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc 8 5.304315000 4.744259000 3.129358000 6 7.978655000 3.742235000 0.694463000 6 6.926338000 3.793167000 0.423026000 6 5.763719000 4.530505000 0.265390000

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59 6 6. 499761000 5.500663000 1.196249000 6 5.730125000 5.913487000 2.434560000 8 7.719192000 4.825256000 1.564910000 1 8.981488000 3.827553000 0.271614000 1 6.667808000 2.798341000 0.78 9451000 8 7.439937000 4.596248000 1.482077000 1 6.698284000 5.167864000 1.756120000 1 5.138643000 3.845015000 0.842924000 1 6.752635000 6.405636000 0.628001000 1 4.873012000 6. 519562000 2.106079000 1 6.373284000 6.542263000 3.066248000 8 4.986595000 5.273693000 0.668522000 7 7.947339000 2.468614000 1.457722000 6 8.556411000 1.344684000 0.835563000 8 8.971928000 1.471619000 0.322878000 7 8.651097000 0.186684000 1.548906000 6 8.152530000 0.123292000 2.780026000 7 8.306182000 1.050403000 3.459250000 6 7.509795000 1.226788000 3. 418771000 6 7.433913000 2.388777000 2.714843000 1 8.573672000 1.849440000 2.898071000 1 7.643859000 1.254860000 4.197295000 1 7.093211000 1.147523000 4.414802000 1 6.961875000 3.285347000 3.097369000 8 4.007163000 3.189764000 1.773075000 6 5.611957000 0.176519000 2.111019000 6 4.347098000 0.633574000 2.864856000 6 3.652814000 0.703169000 3.190707000 6 4.847829000 1.646514000 3.387977000 6 4.583080000 3.104305000 3.076029000 8 5.881637000 1.152091000 2.512340000 1 6.451513000 0.832270000 2.356941000 1 3.728050000 1.307880000 2.265861000 8 4.759580000 1.269711000 4.068498000 1 4.172600000 0.909188000 4.760433000 1 3.022089000 1.026645000 2.361685000 1 5.192821000 1.567727000 4.427648000 1 3.897331000 3.516757000 3.824366000 1 5.528407000 3.659583000 3.116688000 8 2.917277000 0.623960000 4.409279000 7 6.035618000 3.050751000 2.040591000 6 6.338555000 3.354030000 0.731973000 7 6.842807000 4.595516000 0.483346000 7 6.214037000 2.486936000 0.255753000 6 5.749219000 1.287001000 0.152498000 6 5.394738000 0.887345000 1.440685000 6 5.469380000 1.840874000 2.486584000 8 5.111552000 1.734743000 3.677749000 7 4.896932000 0.405679000 1.431461000 6 4.950484000 0.775589000 0.171115000 7 5.469513000 0.207780000 0.652164000 1 6.058914000 3.787499000 2.740361000 1 6.621854000 5.351429000 1.118572000 1 6.855389000 4.858243000 0.493756000 1 4.601288000 1.709685000 0.237755000 15 3.517878000 4.646223000 1.169715000 8 3.048617000 5.552902000 2.265279000 8 2.696642000 4.303274000 0.044531000 8 1.135336000 1.028510000 3.599483000 6 1.564389000 4.550024000 1.644652000 6 0.012376000 4.469338000 1.640480000 6 0.289846000 3.507801000 2.830214000 6 1.041189000 3.447439000 3.590927000 6 1.314187000 2.198201000 4.401735000 8 2.039791000 3.588442000 2.570481000 1 1.856632000 5.569087000 1.927427000 1 0.358357000 4.069745000 0.693972000 8 0.547721000 5.754581000 1.849117000 1 1.032458000 5.687056000 2.695506000 1 0.554829000 2.513643000 2.470560000

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60 1 1.089100000 4.307753000 4.277537000 1 0.631821000 2.178901000 5.257862000 1 2.344006000 2.249372000 4.777303000 8 1.306063000 4.062317000 3.660139000 7 3.137235000 6.458235000 2.878017000 6 2.588689000 7.045322000 1.801044000 7 2.213733000 6.493158000 0.641683000 6 2.436452000 5.169630000 0.640949000 6 2.979824000 4.411666000 1.686413000 6 3.3605610 00 5.126459000 2.843023000 7 3.982103000 4.543786000 3.897981000 7 3.051581000 3.074582000 1.337619000 6 2.567581000 3.026317000 0.116491000 7 2.186166000 4.260978000 0.366362000 1 2.431844000 8.118841000 1.887876000 1 4.067126000 3.533360000 3.963063000 1 4.089393000 5.085612000 4.744456000 1 2.469561000 2.139867000 0.490423000 15 1.249746000 0.4431470 00 4.349711000 8 0.820274000 0.334020000 5.781720000 8 0.684775000 1.468184000 3.406817000 8 3.059220000 3.456952000 1.867549000 6 2.179491000 3.021457000 1.758926000 6 3.62216 9000 2.654406000 2.133198000 6 4.350927000 2.967903000 0.804323000 6 3.619483000 4.242073000 0.349451000 6 3.618278000 4.553344000 1.137305000 8 2.267593000 4.100357000 0.8354730 00 1 1.622606000 3.330990000 2.645826000 1 3.707385000 1.600947000 2.418793000 8 3.985935000 3.535799000 3.181014000 1 4.971703000 3.488023000 3.300251000 1 4.176581000 2.14722 4000 0.103690000 1 4.092090000 5.090051000 0.863123000 1 4.649528000 4.725603000 1.458852000 1 3.022503000 5.456411000 1.305518000 8 5.746528000 3.223497000 0.833009000 7 2.049 193000 0.171125000 1.980736000 6 1.515427000 0.995309000 2.940921000 7 2.236736000 1.124360000 4.095669000 7 0.345752000 1.605346000 2.817417000 6 0.237582000 1.383163000 1.61660 9000 6 0.249878000 0.619069000 0.556258000 6 1.528029000 0.000024000 0.679961000 8 2.183828000 0.581509000 0.188127000 7 0.585164000 0.702862000 0.540268000 6 1.561661000 1.479 953000 0.156855000 7 1.416921000 1.932961000 1.149615000 1 3.004977000 0.184657000 2.089658000 1 3.255003000 1.117375000 4.000685000 1 1.898836000 1.873313000 4.688064000 1 2.3 74221000 1.803894000 0.783954000 15 2.883002000 3.514170000 3.502250000 8 3.731200000 4.580318000 4.121916000 8 2.894300000 2.071137000 3.954193000 8 6.185154000 1.063202000 2.086 183000 6 3.694255000 2.111455000 2.918323000 6 4.945179000 2.952728000 2.548812000 6 6.081090000 1.903115000 2.531197000 6 5.521478000 0.823944000 3.458008000 6 6.178063000 0.5 34399000 3.417374000 8 4.144157000 0.754336000 3.067660000 1 3.276073000 2.481677000 3.854728000 1 4.820893000 3.438969000 1.578738000 8 5.179255000 3.924962000 3.560509000 1 6 .144105000 3.903860000 3.713316000 1 6.211691000 1.487685000 1.531938000 1 5.603045000 1.188397000 4.495864000 1 7.204231000 0.411445000 3.785555000 1 5.648256000 1.216817000 4.0 89093000

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61 8 7.281889000 2.480479000 3.027716000 7 2.625621000 2.168240000 1.941638000 6 1.367530000 2.740619000 2.315111000 8 1.170752000 3.028504000 3.503390000 7 0.446227000 2 .945306000 1.339586000 6 0.699958000 2.607276000 0.069176000 7 0.239495000 2.876838000 0.850257000 6 1.949863000 2.008781000 0.330661000 6 2.871420000 1.810510000 0.639353000 1 1.139455000 3.221155000 0.505598000 1 0.252115000 2.381897000 1.743641000 1 2.126490000 1.702246000 1.352640000 1 3.833642000 1.347437000 0.453698000 15 6.827539000 2.579063000 1 .893986000 8 6.693384000 3.303789000 3.223826000 8 8.147723000 2.527314000 1.184041000 8 8.103481000 3.033239000 0.660832000 6 5.265730000 3.005595000 1.833664000 6 6.179055000 3.702905000 2.856694000 6 7.388171000 4.099899000 1.997608000 6 6.706574000 4.456672000 0.664211000 6 7.570014000 4.352732000 0.578794000 8 5.607592000 3.528611000 0.562392000 1 4.218753000 3.203865000 2.058520000 1 6.441487000 3.039714000 3.690413000 8 5.498536000 4.863578000 3.309272000 1 6.189832000 5.522640000 3.501903000 1 8.061152000 3.245098000 1.862232000 1 6.315665000 5.480097000 0.739138000 1 8.379601000 5.092417000 0.517796000 1 6.968777000 4.588818000 1.464252000 8 8.049288000 5.185668000 2.624609000 7 5.420003000 1.536779000 1.821744000 6 4.524948000 0.790881000 2.597254000 8 3.602426000 1.318222000 3.219691000 7 4.755252000 0.561522000 2.608151000 6 5.818381000 1.247125000 2.002434000 8 5.972615000 2.451875000 2.198954000 6 6.662290000 0.407994000 1.171010000 1 7.446463000 0.870145000 0.585186000 6 6.445539000 0.925294000 1.126167000 1 4.071120000 1.129559000 3.155217000 1 7.052076000 1.589609000 0.523349000 15 8.686516000 2.469647000 2.111787000 8 9.568810000 3.496053000 2.757140000 8 9.110209000 1.058860000 1.837206000 1 4.812973000 5.022560000 3.917438000 1 8.781029000 5.480676000 2.059819000 6 B3LYP/6 3 1G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc 8 9.941260000 1.670525000 2.499457000 6 9.116541000 2.658702000 0 .998783000 6 10.591923000 3.052465000 1.216134000 6 11.148230000 3.030268000 0.216339000 6 9.940595000 3.550173000 1.020444000 6 9.877211000 3.094600000 2.464378000 8 8.780243000 3.063112000 0.314179000 1 8.469332000 3.152803000 1.728172000 1 11.105740000 2.369256000 1.899581000 8 10.693610000 4.407325000 1.643556000 1 10.601725000 4.440348000 2.608325000 1 11.372886000 2.003636000 0.515912000 1 9.944539000 4.648560000 0.996290000 1 10.721515000 3.533236000 3.011728000 1 8.945578000 3.451574000 2.918135000 8 12.321782000 3.792151000 0.386932000 7 7.609380000 0.925810000 4.210182000 6 7.646509000 0.437862000 4.370880000 7 7.275474000 0.931748000 5.593663000 7 8.079520000 1.259887000 3.436582000

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62 6 8.451645000 0.618062000 2.304223000 6 8.446889000 0.749131000 2.029569000 6 7.979476000 1.648979000 3.042910000 8 7.868820000 2.873998000 3.023485000 7 8.867025000 0.988834000 0.732694000 6 9.124767000 0.200884000 0.237692000 7 8.886870000 1.222141000 1.149313000 1 7.263258000 1.505059000 4.967484000 1 6.533667000 0.432673000 6.071207000 1 7.114985000 1.932227000 5.577006000 1 9.464181000 0.414329000 0.766037000 8 6.284171000 1.800640000 2.073631000 6 4.890063000 1.609329000 1.650341000 6 6.188318000 2.229365000 2.179473000 6 6.906447000 1.006583000 2.767284000 6 5.742553000 0.170949000 3.309088000 6 6.010543000 1.319973000 3.390166000 8 4.638230000 0.443005000 2.420583000 1 4.061438000 2.312161000 1.751361000 1 6.756412000 2.719482000 1.386253000 8 5.855147000 3.142666000 3.220710000 1 6.579497000 3.069138000 3.869002000 1 7.439195000 0.457179000 1.988702000 1 5.494467000 0.536700000 4.314382000 1 6.881682000 1.474512000 4.037366000 1 5.143210000 1.832207000 3.818433000 8 7.776297000 1.394905000 3.825088000 7 4.975976000 1.260529000 0.213694000 6 4.74296800 0 2.303350000 0.720702000 8 4.636756000 3.461208000 0.290475000 7 4.623765000 1.971381000 2.038341000 6 4.784209000 0.706476000 2.424471000 7 4.615988000 0.401527000 3.742558000 6 5.161432000 0.334552000 1.520222000 6 5.224774000 0.012483000 0.203660000 1 4.126000000 1.111780000 4.273767000 1 4.290329000 0.555255000 3.909973000 1 5.323023000 1.35046500 0 1.849491000 1 5.470418000 0.732223000 0.562338000 15 9.358312000 0.854321000 3.821001000 8 9.956683000 1.398165000 5.083687000 8 9.397038000 0.593800000 3.428657000 8 2.426818 000 2.364466000 1.063482000 6 1.080166000 2.751046000 2.288852000 6 2.509636000 2.367399000 2.749955000 6 3.430963000 2.910815000 1.623554000 6 2.540987000 3.844619000 0.78623100 0 6 2.753911000 3.709836000 0.713737000 8 1.180276000 3.509258000 1.099217000 1 0.594458000 3.324402000 3.078648000 1 2.609546000 1.280243000 2.839579000 8 2.796789000 2.970236 000 4.000587000 1 3.589485000 3.520857000 3.842327000 1 3.794708000 2.084975000 1.013455000 1 2.742823000 4.880748000 1.088018000 1 3.805105000 3.923506000 0.936690000 1 2.1123 36000 4.417120000 1.250346000 8 4.507203000 3.636986000 2.207909000 7 0.207255000 1.592078000 2.034685000 6 0.754124000 1.284642000 2.997594000 8 0.926757000 1.941618000 4.018276 000 7 1.500689000 0.159405000 2.708644000 6 1.447545000 0.645488000 1.559621000 8 2.261785000 1.559290000 1.421679000 6 0.404660000 0.258851000 0.630521000 1 0.311614000 0.8121 74000 0.296738000 6 0.361753000 0.825953000 0.895021000 1 2.271984000 0.009033000 3.346068000 1 1.121378000 1.180301000 0.206967000 15 6.071199000 3.384454000 1.654784000

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63 8 6.92 4001000 4.288270000 2.491921000 8 6.058442000 3.392198000 0.153566000 8 1.848436000 0.372786000 3.034522000 6 2.160452000 3.971089000 1.708754000 6 0.626605000 3.997942000 1.6884 15000 6 0.278059000 2.735432000 2.493661000 6 1.403795000 2.692831000 3.533940000 6 1.724583000 1.322238000 4.097643000 8 2.554663000 3.236293000 2.854873000 1 2.566523000 4.98 2585000 1.741390000 1 0.237947000 3.976805000 0.667275000 8 0.178127000 5.157093000 2.384695000 1 0.588832000 4.864271000 2.911395000 1 0.314981000 1.844279000 1.864005000 1 1. 139914000 3.354305000 4.370416000 1 0.920594000 1.022220000 4.775934000 1 2.663707000 1.372597000 4.664587000 8 0.989880000 2.863036000 3.130084000 7 2.718423000 3.325356000 0.50 1700000 6 2.917169000 4.134314000 0.650431000 8 2.555675000 5.316552000 0.605910000 7 3.506487000 3.563807000 1.742658000 6 3.809078000 2.267926000 1.734355000 7 4.358522000 1. 722461000 2.856015000 6 3.537944000 1.417940000 0.617064000 6 2.992210000 1.993449000 0.482996000 1 4.781424000 2.383196000 3.496868000 1 4.909184000 0.876612000 2.714873000 1 3.732295000 0.357942000 0.651817000 1 2.747945000 1.432719000 1.375681000 15 2.233277000 1.864175000 2.621481000 8 3.408988000 2.262222000 3.477889000 8 1.742325000 0.453162000 2. 510496000 8 4.707123000 3.744038000 0.648891000 6 6.369323000 0.743275000 2.194498000 6 5.028316000 0.308443000 2.812366000 6 4.165002000 1.572224000 2.631524000 6 5.198452000 2.694813000 2.774933000 6 4.838005000 3.980724000 2.056699000 8 6.429849000 2.156321000 2.255246000 1 7.204734000 0.297566000 2.739788000 1 4.624762000 0.574592000 2.307430000 8 5.227329000 0.056671000 4.193919000 1 4.446831000 0.441566000 4.637244000 1 3.692616000 1.603600000 1.645266000 1 5.321157000 2.914198000 3.844076000 1 3.877753000 4.333535000 2.451325000 1 5.592978000 4.745336000 2.258936000 8 3.200803000 1.695587000 3.668285000 7 8.095100000 2.952814000 0.773091000 6 8.323912000 2.727110000 0.563917000 7 9.068826000 3.666498000 1.223277000 7 7.828015000 1.690864000 1.210789000 6 7.136896000 0.851986000 0.405466000 6 6.954414000 0.923310000 0.975377000 6 7.445095000 2.072412000 1.675315000 8 7.367879000 2.366043000 2.869865000 7 6.241032000 0.174310000 1.427009000 6 5.981351000 0.879960000 0.346619000 7 6.508200000 0.306945000 0.800039000 1 8.452289000 3.801615000 1.197644000 1 9.849849000 4.054028000 0.702659000 1 9.330053000 3.378049000 2.159089000 1 5.431378000 1.808426000 0.316923000 15 1.614894000 1.242237000 3.346093000 8 0.882097000 1.424395000 4.639739000 8 1.204131000 1.878654000 2.050930000 8 7.853609000 4.028909000 3.287384000 6 10.209917000 2.607832000 0.451083000 6 8.984906000 2.784884000 0.464259000

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64 6 8.073928000 3.625029000 0.433732000 6 9.061955000 4.519208000 1.185461000 6 8.549692000 5.014810000 2.538800000 8 10.242081000 3.702658000 1.347136000 1 11.130757000 2.553541000 0.136924000 1 8.547678000 1.816161000 0.720732000 8 9.380045000 3.493808000 1.624914000 1 8.547044000 3.714922000 2.078548000 1 7.572013000 2.957053000 1.135474000 1 9.314659000 5.381066000 0.553759000 1 7.911648000 5.891482000 2.353303000 1 9.403176000 5.346950000 3.139322000 8 7.137561000 4.403205000 0.288307000 7 11.405983000 2.419185000 0.776494000 6 11.642036000 1.502773000 0.181667000 7 11.293213000 0.213105000 0.209568000 6 10.647713000 0.144818000 0.912789000 6 10.355532000 0.680855000 2.006625000 6 10.755413000 2.027862000 1.892954000 7 10.509861000 2.940383000 2.873655000 7 9.677350000 0.020065000 2.990178000 6 9.561812000 1.234913000 2.500113000 7 10.132185000 1.377289000 1.246763000 1 12.1712150 00 1.873386000 1.056928000 1 9.697625000 2.769528000 3.457068000 1 10.678830000 3.909639000 2.634615000 1 9.076164000 2.073818000 2.983717000 15 5.627623000 4.676423000 0.361324000 8 5.318415000 6.128170000 0.156347000 8 5.545367000 4.008124000 1.716539000 1 12.211455000 4.570108000 0.190634000 1 6.965452000 3.946239000 2.861453000 5:6 B3LYP/6 3 1G* opt EmpiricalDispe rsion=GD3 SCRF(PCM) nosymm scf=xqc 8 2.967438000 6.626103000 3.631989000 6 5.401715000 4.965276000 1.249080000 6 6.364616000 4.756038000 2.423080000 6 5.684977000 5.594727000 3.517212000 6 5.176121000 6.792897000 2.707843000 6 4.006938000 7.545846000 3.307769000 8 4.816978000 6.239720000 1.420706000 1 5.927711000 4.914856000 0.294148000 1 6.481225000 3.701270000 2.669826000 8 7.620671000 5.334668000 2.083369000 1 7.922320000 5.789373000 2.891403000 1 4.851733000 5.049973000 3.968270000 1 6.003518000 7.500780000 2.568167000 1 4.3725840 00 8.066590000 4.205127000 1 3.662469000 8.302151000 2.588964000 8 6.596566000 6.038215000 4.512780000 7 4.335264000 3.925666000 1.207421000 6 4.673972000 2.671501000 0.662738000 8 5.867051000 2.462217000 0.366505000 7 3.691725000 1.758804000 0.469867000 6 2.438904000 1.999067000 0.888999000 7 1.510567000 1.061299000 0.659185000 6 2.094943000 3.2307350 00 1.534217000 6 3.067754000 4.172312000 1.649202000 1 1.763920000 0.161425000 0.234364000 1 0.576165000 1.177034000 1.022931000 1 1.090539000 3.422033000 1.890732000 1 2.89632 6000 5.143997000 2.096631000 8 4.843811000 8.369527000 2.529958000 6 6.647206000 5.419433000 0.871110000 6 7.440944000 5.202017000 2.175128000 6 7.060909000 6.449537000 2.9869750 00 6 6.994977000 7.510861000 1.876133000 6 6.177488000 8.745027000 2.182237000 8 6.441944000 6.814953000 0.738411000 1 7.183448000 5.027359000 0.002039000

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6 7 7 0.51 7774000 4.755677000 4.585071000 6 0.492786000 3.815548000 4.419143000 8 0.251671000 2.605785000 4.544769000 6 1.782982000 4.380831000 4.095166000 1 2.617403000 3.716140000 3.9143 35000 6 1.935240000 5.728215000 4.054999000 1 1.479380000 4.399669000 4.795902000 1 2.880522000 6.200564000 3.821381000 15 1.700159000 9.386597000 0.250065000 8 2.175482000 10.53 2879000 1.092643000 8 2.072558000 7.952139000 0.497495000 8 6.666726000 4.998519000 11.037206000 6 4.326775000 6.527284000 8.552150000 6 3.732425000 7.535068000 9.530593000 6 4. 618341000 7.292427000 10.765388000 6 5.989624000 7.116577000 10.100855000 6 7.057894000 6.357506000 10.861549000 8 5.702783000 6.444589000 8.852104000 1 4.195757000 6.829946000 7.50 9872000 1 2.670350000 7.368350000 9.704598000 8 3.964198000 8.844445000 9.020094000 1 4.204509000 9.387233000 9.793582000 1 4.317876000 6.383421000 11.294900000 1 6.388930000 8. 116111000 9.882227000 1 7.217163000 6.848385000 11.829862000 1 7.991936000 6.414708000 10.292433000 8 4.622321000 8.414881000 11.638814000 7 0.030017000 4.079655000 7.935877000 6 0.261149000 5.415806000 7.817303000 7 0.755061000 6.244630000 7.471088000 7 1.476580000 5.912989000 7.999700000 6 2.362270000 4.979440000 8.402489000 6 2.156453000 3.619620000 8. 643433000 6 0.870871000 3.076572000 8.336483000 8 0.494800000 1.893164000 8.404155000 7 3.314654000 3.032537000 9.132765000 6 4.194855000 4.008103000 9.171656000 7 3.676821000 5.216770000 8.724304000 1 1.003836000 3.761910000 7.743378000 1 1.729132000 5.934185000 7.568875000 1 0.568113000 7.227176000 7.620928000 1 5.205348000 3.940493000 9.542693000 15 7.788835000 3.914562000 11.608795000 8 8.596581000 4.537642000 12.707023000 8 7.049343000 2.615742000 11.730877000 8 7.467413000 2.669243000 3.965398000 6 5.859737000 4.946871000 6.497969000 6 5.571057000 6.001761000 5.423368000 6 6.339986000 5.419697000 4.224277000 6 7.592823000 4.871084000 4.911960000 6 8.338146000 3.778844000 4.174939000 8 7.122049000 4.389826000 6.191158000 1 5.872281000 5.381364000 7.497982000 1 4.500203000 6.127250000 5.256103000 8 6.164986000 7.231264000 5.824582000 1 6.572681000 7.599316000 5.018917000 1 5.776515000 4.613675000 3.746103000 1 8.291399000 5.701522000 5.079251000 1 8.691620000 4.180580000 3.217825000 1 9.206605000 3.480142000 4.770360000 8 6.707733000 6.411136000 3.276393000 7 4.818274000 3.885412000 6.507741000 6 3.607465000 4.191004000 7.155542000 8 3.458670000 5.339119000 7.619946000 7 2.660792000 3.229795000 7.243981000 6 2.836438000 2.023220000 6.678711000 7 1.877840000 1.113484000 6.861011000 6 4.016567000 1.731995000 5.918003000 6 4.982754000 2.686187000 5.874576000 1 1.052310000 1.338513000 7.425864000

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68 1 1.958584000 0.194949000 6.451940000 1 4.163663000 0.776388000 5.431322000 1 5.914064000 2.550665000 5.340374000 15 5.677991000 6.652325000 1.968310000 8 6.345122000 7.700987000 1.131147000 8 5.224475000 5.319037000 1.453805000 8 2.062985000 8.529977000 11.804652000 6 1.459157000 7.989080000 10.567581000 6 1.964988000 8.752461000 11.805014000 6 0.644994000 9.327882000 12.337412000 6 0.098532000 9.679988000 11.051721000 6 1.605078000 9.738213000 11.194167000 8 0.283456000 8.635739000 10.121641000 1 2.216363000 7.985870000 9.782252000 1 2.431674000 8.066163000 12.504066000 8 2.873467000 9.768899000 11.420281000 1 3.700623000 9.567361000 11.894380000 1 0.100609000 8.531538000 12.853052000 1 0.259257000 10.645751000 10.670195000 1 1.865034000 10.600300000 11.816956000 1 2.066670000 9.852420000 10.207306000 8 0.745105000 10.466001000 13.171197000 7 1.160867000 6.566311000 10.874534000 6 2.2579900 00 5.688099000 10.934993000 8 3.404945000 6.175870000 10.894131000 7 2.015631000 4.358574000 11.022428000 6 0.763330000 3.897678000 11.160654000 7 0.586971000 2.563806000 11.176865000 6 0.346122000 4.791223000 11.295851000 6 0.105545000 6.115631000 11.105826000 1 1.349082000 1.983268000 10.803708000 1 0.344919000 2.211898000 11.002137000 1 1.351369000 4.4272900 00 11.464072000 1 0.883285000 6.866728000 11.131353000 15 3.394038000 8.491402000 12.791194000 8 3.575702000 9.813238000 13.474560000 8 3.319757000 7.174256000 13.504079000 8 7.82489 8000 2.689997000 6.169908000 6 8.324507000 0.617747000 8.043782000 6 8.481446000 1.432725000 6.763078000 6 8.449491000 0.312041000 5.712992000 6 9.303463000 0.755112000 6.4098170 00 6 9.143637000 2.184660000 5.930164000 8 8.961108000 0.630345000 7.809859000 1 8.780166000 1.115161000 8.903252000 1 7.697056000 2.181572000 6.654119000 8 9.764997000 2.05075 8000 6.774906000 1 10.122363000 1.941205000 5.874965000 1 7.430620000 0.049815000 5.547425000 1 10.359448000 0.483835000 6.275395000 1 9.339107000 2.195132000 4.850841000 1 9.893 892000 2.817346000 6.412706000 8 9.051799000 0.708758000 4.490483000 7 4.192885000 2.665861000 10.148930000 6 5.448297000 3.201866000 9.977642000 7 5.631504000 4.462733000 10.41472 6000 7 6.460879000 2.532198000 9.431135000 6 6.100177000 1.298432000 9.021602000 6 4.856859000 0.669739000 9.121541000 6 3.797225000 1.373142000 9.768782000 8 2.647495000 0.968 781000 10.007379000 7 4.883052000 0.574132000 8.509482000 6 6.107370000 0.695785000 8.053230000 7 6.905904000 0.402218000 8.356570000 1 3.444519000 3.262981000 10.552457000 1 4.8 38361000 5.072927000 10.644034000 1 6.527751000 4.885424000 10.223839000 1 6.503992000 1.536083000 7.507164000 15 8.044421000 1.276710000 3.268007000 8 8.965703000 1.607796000 2.134 344000

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69 8 6.849132000 0.377328000 3.161895000 8 2.392997000 9.853249000 15.031880000 6 5.306541000 7.782176000 13.898555000 6 6.042284000 8.136213000 15.198340000 6 5.159750000 9.2 50506000 15.778546000 6 4.720232000 9.994654000 14.504992000 6 3.406779000 10.748406000 14.582748000 8 4.612730000 8.953333000 13.499629000 1 6.013151000 7.479353000 13.126635000 1 6 .133228000 7.268186000 15.862473000 8 7.313082000 8.653330000 14.836051000 1 7.557751000 9.286009000 15.534980000 1 4.288480000 8.822473000 16.287515000 1 5.519248000 10.686246000 14.2 12497000 1 3.518470000 11.590936000 15.278528000 1 3.154553000 11.143406000 13.593157000 8 5.944834000 10.032735000 16.661008000 7 4.354960000 6.661687000 14.059770000 6 4.847286000 5 .380498000 13.789221000 8 6.031253000 5.178175000 13.532236000 7 3.911586000 4.375795000 13.852719000 6 2.563719000 4.499906000 14.180027000 8 1.824489000 3.506765000 14.190267000 6 2.152376000 5.845511000 14.508507000 1 1.126278000 6.035516000 14.793055000 6 3.049466000 6.858102000 14.442294000 1 4.271823000 3.419396000 13.646287000 1 2.773363000 7.880542000 14 .670851000 15 0.788403000 10.258216000 14.819145000 8 0.531239000 11.615469000 15.403061000 8 0.030160000 9.020640000 15.209669000 8 5.534953000 5.204985000 9.911196000 6 7.575596000 2.414275000 11.818470000 6 8.166059000 2.076885000 10.440224000 6 7.680753000 3.279956000 9.628115000 6 7.769423000 4.427828000 10.633470000 6 6.835279000 5.597766000 10.324196000 8 7.443188000 3.820314000 11.903143000 1 8.209747000 2.032113000 12.623768000 1 7.759963000 1.130246000 10.080676000 8 9.578487000 2.025408000 10.527180000 1 9.872394000 1.873779000 9.610353000 1 6.635996000 3.112045000 9.361353000 1 8.805141000 4.791050000 10.672711000 1 7.323653000 6.216431000 9.556398000 1 6.725425000 6.211774000 11.224370000 8 8.463746000 3.552989000 8.480648000 7 4.891521000 1.731015000 13.298204000 6 6.214304000 1.527785000 13.167958000 7 6.844862000 0.425620000 12.758583000 6 5.969448000 0.546873000 12.440278000 6 4.573386000 0.470654000 12.492160000 6 4.025341000 0.741397000 12.969245000 7 2.705260000 0.936955000 13.139611000 7 3.995736000 1.654548000 12.067945000 6 5.019243000 2.427245000 11.772759000 7 6.243011000 1.818915000 11.989362000 1 6.832820000 2.385341000 13.423334000 1 2.077050000 0.327984000 12.634866000 1 2.361636000 1.865785000 13.398942000 1 4.966807000 3.434458000 11.380149000 15 7.715968000 4.068098000 7.086235000 8 8.580625000 5.144891000 6.504091000 8 6.240548000 4.260296000 7.359042000 1 8.844303000 6.524825000 3.682044000 1 2.190411000 7.133032000 3.913241000 1 5.379548000 10.697232000 17.084829000 1 5.628809000 4.887495000 8.980682000 7 B3LYP/6 3 1G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=xqc

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70 8 32.093160000 11.033630000 2.241830000 6 31.694833000 7.504587000 1.029685000 6 32.692848000 7.068525000 2.119438000 6 32.777675000 8.323303000 3.002510000 6 31.333934000 8.859443000 2.927409000 6 31.188848000 10.356691000 3.110750000 8 30.851258000 8.473236000 1.619075000 1 31.108125000 6.652433000 0.676775000 1 33.655415000 6.758037000 1.701071000 8 32.120495000 6.056947000 2.943601000 1 32.291779000 5.191034000 2.542409000 1 33.458063000 9.051856000 2.555256000 1 30.724324000 8.353236000 3.687984000 1 31.411916000 10.597570000 4.158524000 1 30.163607000 10.663455000 2.879355000 8 33.227442000 8.068529000 4.314429000 7 33.420653000 6.507433000 3.619906000 6 32.812059000 5.672020000 2.712266000 7 32.566525000 4.389497000 3.110100000 7 32.417527000 6.071137000 1.517708000 6 32.662463000 7.384452000 1.295337000 6 33.272113000 8.316497000 2.135779000 6 33.710352000 7.889885000 3.431766000 8 34.260563000 8.525863000 4.328955000 7 33.334898000 9.559793000 1.527096000 6 32.781947000 9.382961000 0.348942000 7 32.349311000 8.076917000 0.150393000 1 33.684823000 6.147611000 4.531152000 1 33.157650000 3.977086000 3.820424000 1 32.313057000 3.758463000 2.360618000 1 32.625093000 10.140293000 0.407967000 8 29.356810000 16.573212000 1.365260000 6 28.932447000 13.527745000 0.733238000 6 30.057216000 12.812203000 0.051464000 6 30.250544000 13.771792000 1.239858000 6 28.820215000 14.247889000 1.506468000 6 28.665409000 15.608264000 2.158875000 8 28.208836000 14.290718000 0.204906000 1 28.268224000 12.813762000 1.211454000 1 30.969631000 12.695780000 0.542736000 8 29.600754000 11.568308000 0.542581000 1 30.866213000 14.610343000 0.897822000 1 28.30409600 0 13.500385000 2.120870000 1 29.085055000 15.570872000 3.172691000 1 27.600381000 15.850704000 2.211630000 8 30.783383000 13.225443000 2.429919000 7 29.430373000 14.397395000 1.820009000 6 29.513663000 13.831547000 3.118898000 8 29.299747000 12.618484000 3.257645000 7 29.818183000 14.660155000 4.158722000 6 30.101348000 15.943855000 3.932946000 7 30.412828000 16.71519500 0 5.011026000 6 30.091662000 16.521063000 2.626697000 6 29.721092000 15.707603000 1.601381000 1 30.068191000 16.389163000 5.906917000 1 30.363147000 17.718970000 4.894762000 1 30.301690 000 17.566997000 2.442570000 1 29.612974000 16.067356000 0.585766000 15 32.349146000 12.658563000 2.456766000 8 32.847854000 12.898751000 3.854088000 8 33.082154000 13.116245000 1.22776900 0 8 26.219766000 20.805263000 1.213484000 6 25.347728000 16.972066000 1.687363000 6 26.340729000 16.620192000 0.558302000 6 26.745801000 18.028446000 0.107054000 6 25.399400000 18.743815 000 0.163981000 6 25.412768000 20.252579000 0.167614000 8 24.791428000 18.222386000 1.370757000 1 24.557706000 16.224583000 1.789488000 1 27.167326000 16.004977000 0.905800000

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71 8 25.6773 21000 15.991280000 0.524707000 1 27.427322000 18.458304000 0.848106000 1 24.796556000 18.425886000 0.696211000 1 25.842450000 20.569083000 0.792040000 1 24.389674000 20.618520000 0.230068 000 8 27.299774000 18.122115000 1.190025000 7 26.031603000 17.046135000 3.015544000 6 26.476577000 15.840464000 3.548549000 8 26.357724000 14.766244000 2.963015000 7 27.066272000 15.9471 72000 4.791479000 6 27.275069000 17.110584000 5.551212000 8 27.867452000 17.040008000 6.630327000 6 26.745169000 18.297699000 4.925025000 1 26.828149000 19.245399000 5.439961000 6 26.15 6749000 18.227768000 3.703845000 1 27.504127000 15.096419000 5.132197000 1 25.740880000 19.106433000 3.222808000 15 28.950123000 18.181578000 1.397467000 8 29.152338000 18.734612000 2.7784 71000 8 29.605504000 18.756952000 0.171348000 8 23.553729000 25.729834000 2.546812000 6 20.813957000 22.399569000 1.999624000 6 22.190564000 21.677280000 2.145745000 6 23.194759000 22.85 1265000 2.083812000 6 22.420951000 23.889808000 1.274841000 6 22.933315000 25.323020000 1.328425000 8 21.094446000 23.787744000 1.813632000 1 20.297692000 21.992407000 1.129860000 1 22. 275471000 21.127300000 3.087337000 8 22.401809000 20.810429000 1.045551000 1 23.317599000 23.240285000 3.097793000 1 22.406272000 23.585846000 0.215549000 1 23.716630000 25.415585000 0.57 0799000 1 22.119939000 26.006926000 1.066753000 8 24.444391000 22.590167000 1.473463000 7 19.901353000 22.259743000 3.125524000 6 18.776878000 21.392010000 3.006742000 8 18.627600000 20. 734313000 1.966953000 7 17.905957000 21.331031000 4.053030000 6 18.148061000 22.012468000 5.171934000 7 17.272145000 21.885682000 6.203388000 6 19.306653000 22.838525000 5.338675000 6 2 0.151154000 22.943842000 4.279901000 1 16.357429000 21.513288000 5.978163000 1 17.250454000 22.647515000 6.876997000 1 19.496664000 23.373271000 6.259379000 1 21.035222000 23.580905000 4. 296284000 15 25.603532000 21.800164000 2.379834000 8 26.713177000 22.753334000 2.731025000 8 24.894316000 21.020488000 3.461804000 8 20.675427000 27.440568000 7.089937000 6 17.980774000 2 7.347107000 4.482876000 6 18.953120000 26.615307000 3.533076000 6 20.297311000 26.812008000 4.248924000 6 20.130658000 28.204249000 4.876061000 6 20.960352000 28.460131000 6.117249000 8 18.730985000 28.289352000 5.219457000 1 17.193296000 27.838563000 3.907619000 1 18.681805000 25.561441000 3.426454000 8 18.911440000 27.282769000 2.281578000 1 20.385236000 26.063402000 5.041879000 1 20.372489000 28.962166000 4.118286000 1 22.019737000 28.412881000 5.848987000 1 20.729557000 29.453787000 6.512066000 8 21.405673000 26.731807000 3.370602000 7 13.902437000 24.453025000 4.986823000 6 14.084356000 25.559461000 4.190774000 7 13.079733000 25.848492000 3.305135000 7 15.177382000 26.292287000 4.224196000 6 16.065598000 25.872421000 5.153780000

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72 6 15.918920000 24.857716000 6.097606000 6 14.759741000 24.021911000 6.029608000 8 14.455809000 23.036585000 6.707693000 7 17.030983000 24.796459000 6.922071000 6 17.839404000 25.730575000 6.470534000 7 17.303903000 26.423212000 5.395379000 1 13.068470000 23.889394000 4.864919000 1 12.134479000 25.719681000 3.654295000 1 13.205219000 26.745590000 2.850271000 1 18.803077000 25.988042000 6.886211000 15 22.815697000 26.071258000 3.974287000 8 23.653458000 27.137185000 4.627416000 8 22.477265000 24.814092000 4.741859000 8 17.571759000 26.859006000 10.979478000 6 15.388308000 29.042588000 8.522560000 6 16.655589000 29.110247000 7.652086000 6 17.694678000 28.534599000 8.615181000 6 17.238833000 29.090029000 9.967828000 6 17.679308000 28.260969000 11.174325000 8 15.798083000 29.135068000 9.874033000 1 14.697842000 29.851383000 8.266762000 1 16.548072000 28.520898000 6.736685000 8 16.921703000 30.473075000 7.363073000 1 17.865424000 30.505462000 7.124996000 1 17.611447000 27.446348000 8.612304000 1 17.615704000 30.115781000 10.074723000 1 18.713999000 28.545436000 11.415762000 1 17.052999000 28.528687000 12.032032000 8 19.014614000 28.947885000 8.311707000 7 11.522946000 26.571618000 6.121492000 6 12.009800000 27.819898000 5.984762000 7 13.034545000 28.392857000 6.622718000 6 13.584697000 27.556028000 7.517775000 6 13.174078000 26.245518000 7.795405000 6 12.094886000 25.755646000 7.032336000 7 11.609890000 24.493182000 7.191755000 7 13.963544000 25.676163000 8.780545000 6 14.8273080 00 26.618830000 9.088108000 7 14.652249000 27.783010000 8.358228000 1 11.508109000 28.433482000 5.239566000 1 12.260082000 23.795025000 7.536502000 1 10.956316000 24.171948000 6.488419000 1 15.613923000 26.544038000 9.829442000 15 20.285787000 27.908707000 8.619415000 8 21.382305000 28.736824000 9.217070000 8 19.747509000 26.661657000 9.288418000 1 32.848447000 7.2024870 00 4.553597000 1 18.338578000 26.617089000 10.403633000 6 19.032585000 26.405320000 1.155299000 1 19.945075000 25.807979000 1.231152000 1 19.126611000 27.074167000 0.293277000 6 16.51881 5000 25.806046000 1.266915000 6 17.832158000 25.502795000 1.015742000 16 18.003521000 23.818898000 0.584300000 6 16.294014000 23.551887000 0.723463000 6 15.638330000 24.692858000 1.1008020 00 1 16.196027000 26.784633000 1.600719000 1 15.882562000 22.570143000 0.528531000 1 14.568740000 24.742129000 1.274531000 6 21.778492000 19.530237000 1.196094000 1 20.706633000 19.66423 2000 1.403491000 1 22.232518000 18.988484000 2.037132000 6 22.229911000 17.395028000 0.171367000 6 21.990518000 18.737591000 0.055790000 16 21.935699000 19.495625000 1.631086000 6 22.241 506000 17.977659000 2.426276000 6 22.371753000 16.956842000 1.525260000 1 22.327802000 16.742484000 0.689083000 1 22.325346000 17.937695000 3.504386000 1 22.579950000 15.931242000 1.81053 0000

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73 6 25.195159000 14.668492000 0.252623000 1 24.134368000 14.735204000 0.031978000 1 25.743364000 14.217403000 0.578475000 6 25.831803000 12.522639000 1.516349000 6 25.360984000 13.806 520000 1.463988000 16 24.920771000 14.374362000 3.060279000 6 25.383791000 12.857746000 3.779602000 6 25.842514000 11.976970000 2.839213000 1 26.179489000 11.990058000 0.638773000 1 25.3 02954000 12.719107000 4.849815000 1 26.192064000 10.976865000 3.070405000 6 29.452429000 10.552291000 0.473166000 1 30.104263000 9.727556000 0.186274000 1 29.763015000 10.936070000 1.450 351000 6 27.100162000 10.408680000 1.530647000 6 28.026093000 10.106457000 0.564545000 16 27.307959000 9.130766000 0.697489000 6 25.760332000 9.155027000 0.093289000 6 25.804741000 9.8 63901000 1.263242000 1 27.350014000 11.010330000 2.399058000 1 24.915492000 8.643385000 0.348973000 1 24.946009000 9.998419000 1.912052000 8 B3LYP/6 3 1G* opt EmpiricalDispersion=GD3 SCRF(PCM) nosymm scf=x qc 8 33.193965000 17.440126000 10.992998000 6 34.378316000 13.828943000 12.048257000 6 33.461348000 13.974682000 13.269500000 6 33.058111000 15.438526000 13.118209000 6 34.372215000 16.08994 2000 12.688460000 6 34.230392000 17.423148000 11.961592000 8 34.976238000 15.092033000 11.828624000 1 35.143873000 13.068465000 12.212603000 1 32.612950000 13.289503000 13.230653000 8 34.249 890000 13.775214000 14.437948000 1 33.801476000 14.262188000 15.151161000 1 32.337017000 15.512022000 12.302813000 1 35.012377000 16.224579000 13.570074000 1 34.065472000 18.197337000 12.72406 9000 1 35.173325000 17.647788000 11.450791000 8 32.539710000 15.998710000 14.316223000 7 33.613109000 13.421621000 10.839357000 6 33.229989000 12.055737000 10.754859000 8 33.493160000 11.314 513000 11.709309000 7 32.591262000 11.634251000 9.624864000 6 32.359124000 12.491702000 8.632853000 7 31.807631000 11.994863000 7.494892000 6 32.691340000 13.880157000 8.711531000 6 33.3 13203000 14.302424000 9.845279000 1 31.383996000 11.078155000 7.547293000 1 31.412496000 12.629407000 6.815338000 1 32.442468000 14.574759000 7.920246000 1 33.579369000 15.337273000 10.021 182000 8 30.031329000 15.786988000 13.845319000 6 29.632088000 12.822292000 11.603941000 6 28.164143000 12.612500000 12.028835000 6 28.068044000 13.650071000 13.156332000 6 29.419948000 13.4 68034000 13.848697000 6 29.908070000 14.635343000 14.680785000 8 30.339288000 13.225195000 12.757204000 1 30.092179000 11.924082000 11.185406000 1 27.471540000 12.794229000 11.206943000 8 27 .951718000 11.323432000 12.574449000 1 28.024774000 14.648655000 12.709548000 1 29.372400000 12.577454000 14.488712000 1 29.181093000 14.818943000 15.481970000 1 30.872365000 14.384872000 15.1 34729000 8 27.004313000 13.473840000 14.066753000 7 28.703914000 13.736703000 6.744322000 6 28.556032000 12.577982000 7.472107000 7 28.091579000 11.483134000 6.787267000

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74 7 28.881179000 12 .483773000 8.743881000 6 29.334823000 13.653951000 9.259950000 6 29.459413000 14.895956000 8.635970000 6 29.114382000 15.005967000 7.248997000 8 29.134062000 15.983505000 6.505149000 7 29.888660000 15.853129000 9.536684000 6 30.021042000 15.205747000 10.674550000 7 29.710512000 13.859653000 10.562965000 1 28.437788000 13.739078000 5.764997000 1 27.318473000 11.664337000 6 .151211000 1 27.923313000 10.685185000 7.389492000 1 30.303580000 15.638406000 11.621279000 15 31.167621000 16.937413000 14.178308000 8 30.954328000 17.555220000 15.523656000 8 31.250122000 17.748483000 12.903899000 8 24.963108000 13.562664000 12.507967000 6 25.275596000 12.106036000 9.099870000 6 23.759438000 11.902643000 8.965467000 6 23.315156000 12.296548000 10.380876000 6 24.392871000 11.622197000 11.228598000 6 24.642248000 12.176027000 12.613226000 8 25.595794000 11.797140000 10.433225000 1 25.850588000 11.466493000 8.428412000 1 23.322301000 12.545777000 8.202253000 8 23.452916000 10.540775000 8.735175000 1 23.408754000 13.382173000 10.477279000 1 24.177356000 10.551339000 11.314290000 1 23.740837000 12.030324000 13.222228000 1 25.475974000 11.628039000 13.065133000 8 22.009748000 11.893556000 10.740326000 7 25.767017000 15.423850000 5.237667000 6 25.556594000 14.100024000 5.273143000 7 25.484668000 13.291073000 6.339134000 6 25.628841000 13.983078000 7.484027000 6 25.834096000 15.359406000 7.611524000 6 25.911509000 16.087396000 6.404891000 7 26.087458000 17.430866000 6.376161000 7 25.946293000 15.719483000 8.944480000 6 25.805252000 14.587922000 9.604490000 7 25.626672000 13.494772000 8.771965000 1 25.442332000 13.617489000 4.304767000 1 26.460815000 17.871520000 7.206166000 1 26.366009000 17.837437000 5.492758000 1 25.805433000 14.474088000 10.679660000 15 25.598920000 14.344298000 13.825229000 8 24.763317000 14.076002000 15.041714000 8 25.933711000 15.720744000 13.324770000 8 20.643999000 12.336297000 8.598368000 6 20.142068000 12.258135000 5.068697000 6 18.607912000 12.266042000 5.229550000 6 18.425522000 11.745390000 6.675468000 6 19.670861000 10.879624000 6.935314000 6 20.237718000 10.989999000 8.337609000 8 20.649915000 11.258857000 5.930547000 1 20.426498000 12.012199000 4.041451000 1 18.190947000 13.262821000 5.115828000 8 17.96386700 0 11.507752000 4.216399000 1 18.420550000 12.599446000 7.356951000 1 19.418854000 9.826882000 6.765143000 1 19.449396000 10.685832000 9.038002000 1 21.094354000 10.323221000 8.463291000 8 17.250231000 10.971898000 6.833172000 7 20.116880000 17.361849000 4.515399000 6 19.228429000 16.440110000 4.018029000 7 18.193703000 16.938367000 3.256691000 7 19.351997000 15.14305800 0 4.207038000 6 20.412609000 14.815838000 4.986542000 6 21.351864000 15.673375000 5.562203000 6 21.207791000 17.085925000 5.376776000 8 21.879043000 18.004271000 5.851304000

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75 7 22.279167 000 14.964458000 6.305146000 6 21.903846000 13.714731000 6.179665000 7 20.763120000 13.553074000 5.415183000 1 19.904129000 18.347075000 4.402459000 1 17.719689000 17.724115000 3.70101600 0 1 17.530661000 16.207880000 3.018394000 1 22.389704000 12.862569000 6.613112000 15 20.750558000 12.831433000 10.173181000 8 19.534884000 12.400365000 10.936991000 8 21.210018000 14.266983 000 10.108779000 8 14.783663000 11.595943000 6.921689000 6 15.994053000 15.646964000 6.045270000 6 14.555833000 15.842138000 6.612525000 6 14.030517000 14.393697000 6.695334000 6 14.8209 25000 13.702521000 5.586618000 6 14.858088000 12.179393000 5.620889000 8 16.135925000 14.258852000 5.743476000 1 16.089346000 16.248810000 5.140431000 1 14.550001000 16.329147000 7.589931 000 8 13.785580000 16.574449000 5.675276000 1 14.356183000 13.963349000 7.648211000 1 14.412847000 14.006469000 4.609509000 1 13.966193000 11.823107000 5.095754000 1 15.743033000 11.8277 21000 5.080102000 8 12.641676000 14.214014000 6.489854000 7 17.087130000 16.041255000 6.920898000 6 17.771463000 17.259398000 6.679844000 8 17.298710000 18.065370000 5.852448000 7 18.93 5645000 17.472877000 7.337595000 6 19.377222000 16.587435000 8.237262000 7 20.615380000 16.757256000 8.752658000 6 18.582272000 15.474657000 8.663253000 6 17.462138000 15.216548000 7.9438 54000 1 21.238522000 17.352555000 8.216943000 1 21.021983000 15.948043000 9.229472000 1 18.906088000 14.816745000 9.456063000 1 16.860307000 14.326466000 8.111104000 15 16.055344000 11.31 7622000 7.936827000 8 15.724065000 10.046164000 8.663756000 8 16.417159000 12.565421000 8.703781000 8 10.380939000 15.283738000 6.815742000 6 9.601417000 19.149512000 7.244724000 6 8. 240624000 18.834630000 6.603868000 6 8.437221000 17.381710000 6.158916000 6 9.901592000 17.403212000 5.700817000 6 10.624222000 16.073633000 5.648037000 8 10.549826000 18.300626000 6.63 6966000 1 9.867151000 20.196607000 7.085997000 1 7.411081000 18.966411000 7.306686000 8 8.101030000 19.682958000 5.472937000 1 7.586150000 19.175290000 4.820058000 1 8.325719000 16. 701692000 7.012042000 1 9.949623000 17.854133000 4.700912000 1 10.241205000 15.521221000 4.778363000 1 11.691168000 16.242450000 5.494776000 8 7.504266000 17.094780000 5.130052000 7 9.596240000 18.915496000 8.713645000 6 8.932187000 19.871246000 9.478189000 8 8.362604000 20.836480000 8.977846000 7 8.965806000 19.635744000 10.837773000 6 9.590836000 18.571374000 11. 519298000 8 9.524507000 18.506513000 12.744941000 6 10.266378000 17.652696000 10.630716000 1 10.800749000 16.809102000 11.046196000 6 10.249095000 17.852715000 9.290434000 1 8.480633000 2 0.319673000 11.408478000 1 10.771237000 17.183885000 8.617513000 15 11.602207000 14.632387000 7.723690000 8 11.022855000 13.394419000 8.349898000 8 12.273807000 15.684279000 8.573434000

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76 1 32.363893000 17.554368000 11.516512000 1 7.651429000 16.189604000 4.813562000 1 14.901014000 18.264842000 6.155318000 6 13.885353000 18.002311000 5.835135000 1 13.165968000 18.334421000 6.593462000 6 13.566454000 18.653088000 4.529524000 16 14.642495000 18.476269000 3.157113000 6 13.598927000 19.438128000 2.152152000 1 13.861818000 19.625173000 1.119101000 6 12.496222000 19.866862000 2.838508000 1 11.718935000 20.480051000 2.395304000 1 11.686379000 19.631425000 4.904527000 6 12.476928000 19.413466000 4.195273000 6 18.245332000 10.098785000 4.145102000 6 17.601179000 9.558842000 2.911267000 16 18.078663000 10.104209000 1.317699000 6 16.922131000 9.051274000 0.557574000 1 16.829273000 9.036736000 0.520552000 6 16.215476000 8.330046000 1.479980000 1 15.442238000 7.616912000 1.215754000 1 16.158159000 8.163421000 3.700277000 6 16.602219000 8.625867000 2.824695000 1 19.330400000 9.929498000 4.128817000 1 17.829140000 9.583875000 5.016003000 6 23.588782000 10.149306000 7.358881000 6 23.161077000 8.726588000 7.220459000 16 23.934690000 7.440664000 8.119511000 6 22.893743000 6.248139000 7.398165000 1 22.990782000 5.206778000 7.676176000 6 22.010863000 6.814216000 6.520375000 1 21.271503000 6.245581000 5.967003000 1 21.559480000 8.874601000 5.788809000 6 22.162076000 8.232924000 6.422790000 1 22.940420000 10.763335000 6.723156000 1 24.625720000 10.296387000 7.027339000 6 28.036098000 10.259053000 11.607590000 6 27.027430000 9.200282000 11.920250000 16 26.989514000 8.401352000 13.477444000 6 25.642172000 7.412551000 12.993882000 1 25.213275000 6.703578000 13.689959000 6 25.255813000 7.683398000 11.710210000 1 24.431176000 7.185232000 11.212467000 1 25.878291000 9.085972000 10.098568000 6 26.047083000 8.706563000 11.100075000 1 27.842849000 10.640567000 10.600628000 1 29.054882000 9.847133000 11.627995000 7:8 B3LYP/6 3 1G* opt EmpiricalDispers ion=GD3 SCRF(PCM) nosymm scf=xqc 8 6.904432000 8.452132000 5.706569000 6 9.730015000 6.250765000 4.448114000 6 9.499290000 6.813064000 3.040277000 6 8.516833000 7.956309000 3.337005000 6 9.065575000 8.493144000 4.663576000 6 8.076033000 9.243808000 5.529842000 8 9.560250000 7.322703000 5.353185000 1 10.730203000 5.826367000 4.546158000 1 9.118984000 6.059843000 2.348328000 8 10.730890000 7.349146000 2.564046000 1 10.498318000 8.191009000 2.130711000 1 7.499555000 7.580170000 3.472735000 1 9.910539000 9.161360000 4.451334000 1 7.844617000 10.191698000 5.021813000 1 8.550100000 9.478419000 6.493119000 8 8.553843000 8.972001000 2.345102000 7 8.765596000 5.163904000 4.770483000 6 9.031950000 3.887726000 4.239519000 8 10.016566000 3.758400000 3.483404000 7 8.214271000 2.860385000 4.570622000 6 7.121698000 3.067899000 5.323933000 7 6.352826000 2.010392000 5.615682000

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77 6 6.807358000 4.367322000 5.836073000 6 7.661551000 5.381464000 5.544026000 1 6.545770000 1.094835000 5.192000000 1 5.439162000 2.157084000 6.019198000 1 5.928240000 4.537322000 6.444971000 1 7.5119620 00 6.396727000 5.890949000 8 8.197481000 6.557957000 0.261111000 6 8.712527000 3.002793000 0.616626000 6 10.214195000 3.262942000 0.817430000 6 10.268026000 4.798174000 0.849075000 6 8.933057000 5.154386000 1.533255000 6 8.361993000 6.506517000 1.157744000 8 8.015122000 4.110448000 1.144569000 1 8.408676000 2.089394000 1.134511000 1 10.815095000 2.8162280 00 0.020575000 8 10.645801000 2.816906000 2.101379000 1 10.874443000 1.871906000 2.053125000 1 10.261506000 5.188255000 0.172110000 1 9.066694000 5.120320000 2.623463000 1 9.06007 5000 7.284800000 1.491432000 1 7.395513000 6.659664000 1.649549000 8 11.403718000 5.319795000 1.503658000 7 8.416548000 0.409234000 3.053003000 6 9.175599000 0.426508000 1.9061200 00 7 9.865750000 1.557347000 1.655470000 7 9.238686000 0.596302000 1.059014000 6 8.513269000 1.653939000 1.477965000 6 7.780429000 1.809676000 2.657452000 6 7.667291000 0.68306 5000 3.524721000 8 7.004774000 0.579650000 4.572933000 7 7.204322000 3.072826000 2.713260000 6 7.564450000 3.650906000 1.591869000 7 8.358933000 2.835505000 0.794929000 1 8.375 098000 1.274373000 3.628614000 1 9.950858000 2.313251000 2.344971000 1 10.498064000 1.539192000 0.868090000 1 7.347999000 4.664331000 1.293397000 8 7.631387000 7.543675000 0.43597 3000 6 8.312355000 3.924408000 0.281619000 6 7.759370000 4.088920000 1.709938000 6 7.601355000 5.610713000 1.751537000 6 8.855504000 6.082272000 1.016838000 6 8.779272000 7.463 935000 0.409005000 8 9.033227000 5.099826000 0.029012000 1 8.971193000 3.057439000 0.208036000 1 6.817345000 3.562381000 1.856168000 8 8.730617000 3.649214000 2.657457000 1 6.7 31247000 5.866794000 1.137833000 1 9.715776000 6.045549000 1.698987000 1 8.716993000 8.205004000 1.214045000 1 9.693147000 7.649604000 0.167595000 8 7.489357000 6.202956000 3.028 120000 7 5.241365000 0.379571000 1.406360000 6 6.062428000 0.400236000 0.304860000 7 6.121120000 0.715197000 0.449362000 7 6.802831000 1.450877000 0.021968000 6 6.616016000 2.4 93553000 0.809714000 6 5.758322000 2.613363000 1.903814000 6 5.006474000 1.457320000 2.280857000 8 4.220203000 1.320908000 3.236074000 7 5.827580000 3.897310000 2.429443000 6 6 .716671000 4.519343000 1.686121000 7 7.241506000 3.706284000 0.691781000 1 4.724808000 0.500774000 1.610766000 1 5.425672000 1.468921000 0.361239000 1 6.623815000 0.636104000 1.3 21832000 1 7.015385000 5.553386000 1.768868000 15 7.318606000 8.979162000 1.202182000 8 7.634034000 10.135593000 0.302107000 8 6.005299000 8.787569000 1.899577000

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78 8 3.414657000 7 .804525000 3.095923000 6 3.662943000 5.385311000 0.301598000 6 5.044549000 5.889712000 0.150272000 6 5.191960000 7.116031000 0.770766000 6 3.772908000 7.692341000 0.730657000 6 3.317451000 8.557919000 1.889684000 8 2.932021000 6.523353000 0.678496000 1 3.125937000 4.864922000 0.483050000 1 5.819019000 5.132437000 0.026809000 8 5.024321000 6.354165000 1 .493750000 1 5.416055000 6.770560000 1.786512000 1 3.655200000 8.263447000 0.199773000 1 3.947980000 9.455107000 1.939248000 1 2.278571000 8.855464000 1.711815000 8 6.136404000 8.080745000 0.355404000 7 3.756275000 4.415098000 1.427468000 6 4.085837000 3.100569000 1.064767000 8 4.444409000 2.897194000 0.113741000 7 3.991966000 2.122789000 1.991396000 6 3.615351000 2.400413000 3.249181000 7 3.515213000 1.373149000 4.102277000 6 3.334104000 3.743618000 3.659289000 6 3.415664000 4.716265000 2.712152000 1 3.695274000 0.412782000 3.789459000 1 3.172678000 1.520957000 5.039654000 1 3.059532000 3.995371000 4.675852000 1 3.227423000 5.758921000 2.928995000 15 7.686840000 7.974099000 0.960305000 8 8.419576000 9.140812000 0.364537000 8 7.637928000 7.685860000 2.433469000 8 5.396221000 4.995972000 3.880537000 6 4.714147000 1.365782000 3.186457000 6 3.905693000 1.186187000 4.485077000 6 4.129882000 2.565282000 5.122683000 6 5.608938000 2.793814000 4.815170000 6 6.110453000 4.219050000 4.841436000 8 5.765147000 2.253934000 3.484948000 1 5.123924000 0.417066000 2.835568000 1 2.857970000 0.949580000 4.297231000 8 4.517601000 0.191171000 5.294709000 1 3.530398000 3.298194000 4.571888000 1 6.209606000 2.203116000 5.519640000 1 5.966793000 4.621435000 5.852330000 1 7.180913000 4.229037000 4.606717000 8 3.880132000 2.666093000 6.507871000 7 1.659702000 0.142776000 0.535745000 6 2.109136000 0.763047000 0.566883000 7 2.861541000 0.245034000 1.536050000 6 3.125949000 1.051153000 1.306897000 6 2.695721000 1.835689000 0.232283000 6 1.944089000 1.160541000 0.757969000 7 1.494183000 1.734542000 1.895759000 7 3.188635000 3.128799000 0.348201000 6 3.905776000 3.113406000 1.454001000 7 3.906764000 1.878209000 2.078402000 1 1.833538000 1.808395000 0.654126000 1 2.00592500 0 2.541391000 2.226959000 1 1.148290000 1.100067000 2.619162000 1 4.441267000 3.950658000 1.881066000 15 5.949605000 6.535254000 3.589436000 8 6.158073000 7.266281000 4.883473000 8 5.096039000 7.054334000 2.468057000 8 1.602235000 6.070142000 5.807081000 6 0.852002000 5.329847000 2.207306000 6 0.328700000 6.308992000 2.140129000 6 0.242819000 6.92642700 0 3.546303000 6 1.271235000 7.123695000 3.672005000 6 1.873031000 7.251488000 5.055850000 8 1.812181000 5.947345000 3.025223000 1 1.287649000 5.114942000 1.232506000

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79 1 1.266711 000 5.809334000 1.926109000 8 0.069102000 7.339883000 1.202488000 1 0.584705000 6.189444000 4.280164000 1 1.555150000 8.010484000 3.091627000 1 1.441633000 8.133729000 5.54626700 0 1 2.955540000 7.391543000 4.959974000 8 0.929783000 8.148184000 3.724278000 7 0.451062000 4.008418000 2.766090000 6 0.198458000 3.149231000 1.881513000 8 0.521498000 3.508009 000 0.746126000 7 0.446218000 1.891097000 2.366488000 6 0.146790000 1.404360000 3.635810000 8 0.431314000 0.238047000 3.940848000 6 0.487972000 2.370436000 4.505337000 1 0.7470 13000 2.086403000 5.516503000 6 0.766321000 3.614155000 4.043456000 1 0.901737000 1.225896000 1.697048000 1 1.239591000 4.368863000 4.658973000 15 2.453034000 8.151357000 4.405227 000 8 2.680440000 9.566806000 4.847726000 8 2.610688000 6.956920000 5.305114000 8 1.533670000 1.665923000 6.672730000 6 0.135746000 1.306521000 4.929558000 6 1.070641000 1.2396 05000 5.891053000 6 0.519702000 0.349410000 7.025969000 6 0.985040000 0.638412000 7.028537000 6 1.868189000 0.517028000 7.450501000 8 1.300832000 1.000754000 5.666186000 1 0.22 1107000 2.300302000 4.489369000 1 1.927675000 0.783505000 5.398984000 8 1.551709000 2.512530000 6.282593000 1 0.667789000 0.697151000 6.741770000 1 1.197397000 1.490017000 7.6881 58000 1 1.706483000 0.717636000 8.516503000 1 2.919532000 0.252283000 7.289054000 8 1.087464000 0.603752000 8.295581000 7 1.744914000 0.886399000 0.286390000 6 1.710051000 1.97 1847000 1.131298000 7 2.347964000 3.086022000 0.723692000 7 1.127558000 1.940998000 2.327414000 6 0.622190000 0.726545000 2.628862000 6 0.634970000 0.440531000 1.870228000 6 1. 220164000 0.387088000 0.568617000 8 1.301714000 1.303072000 0.260694000 7 0.055757000 1.487262000 2.572447000 6 0.296784000 0.965649000 3.728276000 7 0.004870000 0.385256000 3.80 8560000 1 2.185292000 0.992100000 0.650255000 1 2.719130000 3.175599000 0.230028000 1 2.196391000 3.926606000 1.262670000 1 0.750972000 1.489248000 4.557822000 15 2.337315000 3. 082808000 6.993248000 8 2.433423000 3.294179000 8.475555000 8 1.756722000 4.087821000 6.041016000 8 5.385524000 2.405954000 7.463371000 6 5.241391000 3.655543000 3.884502000 6 4.360748000 4.823983000 4.341724000 6 4.419330000 4.625379000 5.858880000 6 5.900250000 4.283969000 6.054859000 6 6.260849000 3.522631000 7.312847000 8 6.222378000 3.484089000 4. 887316000 1 5.719970000 3.851143000 2.929793000 1 3.358931000 4.773575000 3.927728000 8 4.969998000 6.073436000 4.034180000 1 3.816964000 3.749523000 6.119035000 1 6.490818000 5.208221000 6.022432000 1 6.158309000 4.196768000 8.172531000 1 7.306848000 3.202098000 7.252424000 8 4.022845000 5.736662000 6.637981000 7 4.452327000 2.400697000 3.712487000

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80 6 3.635844000 2.306539000 2.570112000 8 3.535267000 3.312793000 1.836088000 7 3.003726000 1.138164000 2.312256000 6 3.106017000 0.095004000 3.158334000 7 2.485539000 1.043868000 2.840849000 6 3.855382000 0.207311000 4.375498000 6 4.530205000 1.365896000 4.595246000 1 2.042213000 1.149747000 1.920397000 1 2.680969000 1.884569000 3.376408000 1 3.898645000 0.607436000 5.085548000 1 5.153179000 1.534019000 5.461783000 15 2.454027000 5.783992000 7.207418000 8 2.400826000 6.992092000 8.095676000 8 2.021387000 4.410200000 7.634501000 8 3.455950000 0.033667000 7.520469000 6 5.945816000 0.130180000 4.638013000 6 6.992058000 0.437999000 5.621566000 6 6.227815000 0.308427000 6.943720000 6 5.505081000 1.027751000 6.765092000 6 4.269627000 1.204758000 7.623063000 8 5.158169000 1.055377000 5.359692000 1 6.417365000 0.623477000 3.786629000 1 7.267431000 1.459884000 5.365020000 8 8.150299000 0.376258000 5.691685000 1 5.484610000 1.108874000 6.994669000 1 6.201072000 1.850886000 6.972401000 1 4.584603000 1.350548000 8.661346000 1 3.699620000 2.079736000 7.292510000 8 7.006891000 0.295533000 8.122604000 7 5.068729000 0.925795000 4.065655000 6 5.514739000 1.602209000 2.917764000 8 6.707443000 1.455799000 2.569973000 7 4.629570000 2.359004000 2.224766000 6 3.375887000 2.536016000 2.674674000 7 2.497407000 3.188825000 1.896987000 6 2.983452000 2.042983000 3.962076000 6 3.842866000 1.207973000 4.599020000 1 2.724374000 3.310679000 0.905013000 1 1.511338000 3.044401000 2.106054000 1 2.010464000 2.263685000 4.377101000 1 3.605709000 0.730466000 5.541404000 15 2.387114000 0.357015000 8.728822000 8 2.865041000 0.182545000 10.044631000 8 2.034011000 1.797553000 8.495934000 8 5.655652000 3.044460000 8.112552000 6 7.492620000 2.421836000 4.903524000 6 7.314015000 0.896759000 5.052388000 6 6.786608000 0.800832000 6.492036000 6 7.579390000 1.916304000 7.191167000 6 6.944986000 2.511477000 8.432459000 8 7.709223000 2.951552000 6.193608000 1 8.3362530 00 2.647398000 4.248051000 1 6.611289000 0.503488000 4.313748000 8 8.598686000 0.308563000 4.893328000 1 5.725537000 1.063276000 6.507825000 1 8.573384000 1.525911000 7.450504000 1 6.836790000 1.727814000 9.189852000 1 7.600226000 3.289998000 8.835360000 8 6.984406000 0.475860000 7.063601000 7 5.378560000 3.175084000 0.441575000 6 6.704300000 3.0137560 00 0.763787000 7 7.573720000 2.876702000 0.264384000 7 7.152849000 3.018456000 2.013510000 6 6.165627000 3.149889000 2.921154000 6 4.809301000 3.379449000 2.706732000 6 4.33567 9000 3.406096000 1.356365000 8 3.176150000 3.585770000 0.954732000 7 4.126360000 3.417174000 3.915690000 6 5.043755000 3.195768000 4.831779000 7 6.313038000 3.036944000 4.2874480 00

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81 1 5.099995000 3.031845000 0.549394000 1 7.244005000 2.486927000 1.157234000 1 8.512252000 2.615091000 0.006167000 1 4.884880000 3.169443000 5.900732000 15 5.916553000 1.04005 1000 8.232594000 8 6.745197000 1.421003000 9.426676000 8 4.728272000 0.126812000 8.301559000 8 8.257910000 2.513220000 7.947128000 6 9.648240000 3.696385000 4.633682000 6 10.504 662000 4.714437000 5.403586000 6 10.337731000 4.242716000 6.854773000 6 10.276995000 2.715008000 6.675578000 6 9.550259000 1.937432000 7.752119000 8 9.593430000 2.524876000 5.41838 4000 1 10.093131000 3.488796000 3.660317000 1 10.163116000 5.743967000 5.240149000 8 11.849358000 4.539167000 4.982732000 1 12.401885000 4.743386000 5.758848000 1 9.392983000 4.610 257000 7.271810000 1 11.302803000 2.333541000 6.588904000 1 10.130583000 1.974901000 8.683565000 1 9.453660000 0.892744000 7.436506000 8 11.449776000 4.699601000 7.606406000 7 8.2 72386000 4.171701000 4.367812000 6 8.060368000 4.820222000 3.148543000 8 8.978490000 5.058225000 2.366864000 7 6.756183000 5.175644000 2.903026000 6 5.660897000 4.999458000 3.744 319000 8 4.537808000 5.389159000 3.398994000 6 5.973420000 4.357125000 5.001953000 1 5.181023000 4.179387000 5.716515000 6 7.247137000 3.976229000 5.263409000 1 6.592356000 5.6 48412000 1.987141000 1 7.522334000 3.484237000 6.189524000 15 7.195741000 1.723436000 8.957417000 8 7.889576000 1.347647000 10.233343000 8 5.930626000 2.531562000 8.901384000 8 3 .372348000 7.250219000 6.775615000 6 6.716673000 7.399401000 4.683873000 6 7.149470000 6.170103000 5.501336000 6 6.052826000 6.136041000 6.566081000 6 5.814778000 7.624349000 6.8 39914000 6 4.432423000 7.957970000 7.398997000 8 6.016928000 8.263507000 5.560369000 1 7.584887000 7.902491000 4.248681000 1 7.176590000 5.268163000 4.884649000 8 8.417642000 6 .442312000 6.077642000 1 8.505647000 5.808522000 6.811710000 1 5.155733000 5.689649000 6.132918000 1 6.584033000 7.982005000 7.537398000 1 4.453727000 7.759835000 8.480613000 1 4.247517000 9.028818000 7.260858000 8 6.446453000 5.451959000 7.742696000 7 6.321807000 6.377276000 0.353545000 6 7.395464000 6.591264000 0.427393000 7 7.426617000 6.826330000 1 .739936000 6 6.186904000 6.838679000 2.263057000 6 4.983523000 6.630763000 1.577830000 6 5.082653000 6.372605000 0.192649000 7 4.011986000 6.145368000 0.597021000 7 3.902401000 6.715265000 2.438023000 6 4.439248000 6.966627000 3.611637000 7 5.821648000 7.053763000 3.573448000 1 8.350511000 6.540870000 0.090063000 1 3.176014000 5.807142000 0.137743000 1 4.171251000 5.826427000 1.557054000 1 3.901330000 7.109589000 4.541238000 15 5.303639000 4.579834000 8.592092000 8 5.624412000 4.767162000 10.043781000 8 3.936424000 4.863492000 8.009935000

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82 1 11.583462000 4.705059000 2.238785000 1 6.317138000 8.913720000 6.324541000 1 11.366071000 4.383935000 8.519870000 1 3.412699000 6.338851000 7.157446000 1 8.689424000 0.474691000 3.857272000 6 8.986424000 0.336742000 4.529531000 1 10.001709000 0.119369000 4.880377000 6 8.951242000 1.648744000 3.795812000 16 8.482698000 3.115613000 4.625608000 6 8.827543000 4.077244000 3.216743000 1 8.660916000 5.146409000 3.233731000 6 9.272266000 3.305295000 2.178417000 1 9.530766000 3.702403000 1.203027000 1 9.646545000 1.143587000 1.811493000 6 9.335329000 1.914300000 2.508580000 6 0.635697000 3.472274000 6.810326000 6 1.092315000 4.832874000 6.367316000 16 2.144149000 4.990849000 4.979886000 6 2.072297000 6.724168000 5.064886000 1 2.618342000 7.320007000 4.345847000 6 1.285417000 7.145690000 6.101957000 1 1.110358000 8.190982000 6.333927000 1 0.074822000 6.188614000 7.707916000 6 0.728188000 6.060684000 6.850754000 1 0.381273000 3.292241000 6.437410000 1 0.601817000 3.402996000 7.905074000 6 4.318562000 1.150701000 4.813703000 6 5.618699000 1.889610000 4.700422000 16 7.057809000 1.147655000 4.020765000 6 7.941766000 2.645188000 4.114442000 1 8.960416000 2.693329000 3.750679000 6 7.176482000 3.640748000 4.651365000 1 7.53617300 0 4.653083000 4.801847000 1 5.097568000 3.852497000 5.424269000 6 5.854678000 3.206569000 4.991496000 1 3.655130000 1.682188000 5.502505000 1 3.810225000 1.126501000 3.841700000 6 8.678515000 2.228883000 2.889358000 6 10.033900000 1.591554000 2.872194000 16 11.251092000 2.019773000 1.690984000 6 12.288853000 0.722864000 2.207381000 1 13.261059000 0.59127800 0 1.751078000 6 11.733489000 0.021198000 3.243709000 1 12.234053000 0.801655000 3.743846000 1 9.841917000 0.097535000 4.418449000 6 10.445334000 0.521448000 3.622703000 1 8.214183 000 2.034516000 3.861352000 1 8.046139000 1.757484000 2.129167000 6 8.583861000 1.040037000 4.420828000 1 7.867719000 1.643379000 4.989309000 1 9.586096000 1.428217000 4.63539200 0 6 8.105940000 0.099143000 2.048829000 6 8.281937000 1.123604000 2.940639000 16 8.063215000 2.672976000 2.152529000 6 7.708182000 1.905148000 0.630990000 6 7.766875000 0.544678 000 0.729401000 1 8.190632000 0.944704000 2.321372000 1 7.480565000 2.507586000 0.235378000 1 7.563527000 0.119245000 0.104845000 6 4.805852000 6.527480000 2.679040000 1 3.8599 92000 6.169811000 2.270341000 1 4.748808000 7.619229000 2.756175000 6 5.804858000 5.390120000 0.594323000 6 5.909907000 6.134901000 1.741111000 16 7.555481000 6.690223000 1.965661 000 6 8.071808000 5.919389000 0.494427000 6 7.034433000 5.277502000 0.126060000 1 4.879056000 4.912843000 0.297351000 1 9.105693000 5.983607000 0.180859000 1 7.140962000 4.7430 50000 1.062864000

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83 6 0.126762000 6.956195000 0.186478000 1 0.234427000 5.870906000 0.282359000 1 1.013420000 7.406115000 0.640338000 6 1.197661000 8.543862000 1.724240000 6 1.09 5530000 7.463590000 0.888405000 16 2.672019000 6.748514000 0.622242000 6 3.442701000 7.918038000 1.650482000 6 2.535355000 8.805789000 2.160927000 1 0.337940000 9.139418000 2.0138 60000 1 4.512314000 7.876586000 1.809563000 1 2.806730000 9.620442000 2.823691000 6 4.815010000 5.343037000 2.495551000 1 5.400615000 5.673261000 3.359108000 1 5.221157000 4.38 2466000 2.163625000 6 2.504921000 6.278384000 3.134641000 6 3.354188000 5.234307000 2.862230000 16 2.472651000 3.724184000 2.819791000 6 0.969327000 4.530360000 3.147639000 6 1. 143843000 5.879749000 3.302560000 1 2.845499000 7.307897000 3.174532000 1 0.050407000 3.960588000 3.173778000 1 0.326853000 6.560339000 3.514258000 CHAPTER IV 1 SCF E(RB3LYP) = 689.132338910 a u B3LYP/6 31G(d) opt 6 0.283266000 0.778090000 0.026854000 6 1.531439000 1.418973000 0.023501000 6 2.704569000 0.659381000 0.024155000 1 3.643692000 1.196802000 0.068940000 6 2.6414 26000 0.737333000 0.026974000 6 0.222372000 0.621945000 0.072585000 6 1.137661000 1.288746000 0.088510000 8 0.860996000 1.547246000 0.006442000 6 2.016787000 0.838609000 0.418536 000 8 2.176317000 0.371551000 0.256751000 6 1.396642000 1.371800000 0.078686000 1 1.364968000 2.457479000 0.104554000 1 2.869735000 1.471251000 0.172331000 1 1.188883000 2.0907 16000 0.653712000 1 1.345616000 1.732953000 1.076633000 1 1.951674000 0.672671000 1.507985000 8 3.733592000 1.561240000 0.031789000 6 5.018305000 0.965908000 0.036497000 1 5.14 6809000 0.384283000 0.959180000 1 5.209332000 0.314573000 0.827097000 1 5.732282000 1.791751000 0.028702000 8 1.658922000 2.780293000 0.142069000 6 1.139601000 3.569581000 0.9309 74000 1 0.050912000 3.494602000 0.996667000 1 1.587986000 3.269507000 1.887701000 1 1.424869000 4.600232000 0.707566000 1* SCF E(RB3LYP) = 689.108444891 au B3LYP/6 31G(d) TD(Root=3,NStates=40) opt 6 0.396609000 0.749754000 0.302260000 6 1.662270000 1.382408000 0.343753000 6 2.849505000 0.605364000 0.251015000 1 3.799664000 1.073874000 0.469663000 6 2.699876000 0.769529000 0.028948000 6 0.269757000 0.707448000 0.286950000 6 1.077039000 1.263178000 0.495533000 8 0.701365000 1.499965000 0.033671000 6 1.991791000 0.852968000 0.271498000 8 2.063603000 0.424147000 0.217738000 6 1.437957000 1.410982000 0.059880000 1 1.401001000 2.449719000 0.383111000 1 2.713814000 1.484401000 0.246456000 1 1.180660000 2.277311000 0.102520000 1 1.429958000 1.259135000 1.553010000 1 2.146894000 0.881704000 1.366445000 8 3.748787000 1.589234000 0.305538000

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84 6 5.056804000 1.034158000 0.378973000 1 5.092043000 0.198639000 1.087394000 1 5.396873000 0.689995000 0.605493000 1 5.704460000 1.842226000 0.723406000 8 1.869444000 2.725583000 0.338428000 6 0.889157000 3.634787000 0.843174000 1 0.114848000 3.836828000 0.099463000 1 0.423412000 3.242064000 1.753743000 1 1.435972000 4.552964000 1.070317000 SCF E(RB3LYP) = 689.064976775 au B3LYP/6 31G* opt=(noeigentest,TS,ver ytight,calcall) int(grid=ultraf ine) 6 0.952742000 0.304233000 0.398263000 6 0.036951000 1.337836000 0.152516000 6 1.354104000 0.99 1522000 0.030320000 1 2.119457000 1.735554000 0.218759000 6 1.777732000 0.375094000 0.020080000 6 0.482300000 1.054373000 0.483444000 6 1.466934000 2.000514000 0.785115000 8 2. 210267000 0.554731000 0.420341000 6 2.996208000 0.630130000 0.967871000 8 2.991958000 1.808453000 0.534094000 6 0.882354000 1.390400000 0.202008000 1 1.185309000 2.430433000 0.23 2790000 1 3.934302000 0.062350000 0.971766000 1 2.276491000 1.718643000 1.443711000 1 1.254567000 3.062545000 0.704420000 8 0.462027000 2.597801000 0.116802000 6 0.448085000 3. 662658000 0.107422000 1 0.945340000 3.567169000 1.082120000 1 1.210683000 3.711222000 0.681363000 1 0.149701000 4.575409000 0.091982000 8 3.118305000 0.526870000 0.243430000 6 3.632702000 1.847472000 0.270296000 1 3.163269000 2.444789000 1.063554000 1 3.487577000 2.354334000 0.693304000 1 4.701159000 1.751642000 0.471938000 1 2.232618000 0.291897000 1. 684557000 2 SCF E(RB3LYP) = 998.817664656 au B3LYP/6 31G(d) opt 6 7.125842000 8.301871000 2.075710000 6 8.169664000 7.695613000 1.335773000 6 9.014905000 8.489080000 0.569731000 1 9.825406000 8.065819000 0.010266000 6 8.830827000 9.883212000 0.523138000 6 6.954621000 9.679007000 2.030882000 6 5.831223000 10.288068000 2.836552000 8 6.326668000 7.480365000 2.833081000 6 5.088532000 8.066666000 3.241117000 6 4.054400000 8.002607000 2.111903000 1 4.412105000 8.568342000 1.243827000 1 3.140795000 8.496732000 2.465256000 8 5.276277000 9.358981000 3.766308000 6 7.804934000 10.479944000 1.247728000 1 7.650785000 11.553424000 1.230843000 1 4.764624000 7.458702000 4.089900000 6 3.744380000 6.555747000 1.679935000 1 4.678884000 6.078634000 1.365247000 1 3.379619000 5.991617000 2.549041000 6 2.721526000 6.492722000 0.565444000 6 1.350553000 6.424063000 0.847746000 6 3.121347000 6.538333000 0.777151000 1 1.021116000 6.380259000 1.884104000 1 4.182080000 6.584516000 1.015479000 6 0.405423000 6.404727000 0.178850000 6 2.180635000 6.519928000 1.807693000 1 0.653000000 6.347052000 0.062475000 1 2.512572000 6.552352000 2.842388000 6 0.817929000 6.453624000 1.511624000 1 0.083812000 6.435525000 2.312797000

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85 1 6.197283000 11.120795000 3.446180000 1 5.046110000 10.688665000 2.174630000 8 8.252285000 6.340417000 1.438736000 6 9.296472000 5.685645000 0.737171000 1 9.211786000 5.837476000 0.347247000 1 10.283920000 6.029853000 1.071849000 1 9.187019000 4.623495000 0.963501000 8 9.724983000 10.554147000 0.268448000 6 9.606096000 11.962967000 0.355006000 1 8.636218000 12.262761000 0.775145000 1 9.734185000 12.440961000 0.625788000 1 10.404592000 12.292113000 1.022921000 2* SCF E(RB3LYP) = 998.764608402 au (not fully converged) B3LYP/6 31G(d) TD(Root=5) opt 6 7.113385000 8.392141000 1.974276000 6 8.273875000 7.757354000 1.450948000 6 9.400656000 8.611617000 1.194323000 1 10.420314000 8.256288000 1.079653000 6 9.131134000 9.963112000 0.873506000 6 6.914533000 9.752923000 1.852029000 6 5.744344000 10.377876000 2.567131000 8 6.206816000 7.570629000 2.665087000 6 5.020175000 8.185370000 3.138468000 6 3.922880000 8.040768000 2.071981000 1 4.168678000 8.644599000 1.192831000 1 2.991176000 8.452800000 2.483396000 8 5.203265000 9.493999000 3.566431000 6 7.908407000 10.552600000 1.189704000 1 7.708975000 11.593830000 0.959258000 1 4.763704000 7.615284000 4.037993000 6 3.736010000 6.558399000 1.673591000 1 4.689920000 6.168345000 1.306505000 1 3.480509000 5.970012000 2.564638000 6 2.672527000 6.405720000 0.639988000 6 1.2943650 00 6.313938000 1.013254000 6 3.012922000 6.365873000 0.749233000 1 1.026576000 6.325043000 2.064552000 1 4.056192000 6.413967000 1.041770000 6 0.315592000 6.197975000 0.055112000 6 2.032619000 6.248050000 1.707611000 1 0.726153000 6.123748000 0.347979000 1 2.302581000 6.213790000 2.757272000 6 0.673448000 6.164807000 1.317924000 1 0.099556000 6.0697670 00 2.073364000 1 6.030187000 11.286736000 3.110368000 1 4.942748000 10.665696000 1.862120000 8 7.998734000 6.519657000 0.785957000 6 9.134390000 5.839998000 0.314091000 1 9.59406 4000 6.351158000 0.546704000 1 9.901497000 5.734317000 1.097004000 1 8.805394000 4.842722000 0.001782000 8 10.154512000 10.639047000 0.236726000 6 9.904541000 11.941359000 0.2477790 00 1 9.083708000 11.942097000 0.977964000 1 9.660237000 12.635992000 0.568202000 1 10.829548000 12.267426000 0.730683000 SCF E(RB3LYP) = 998.760865860 au B3LYP/6 31G* opt=(noeigentest,TS, calcall) int(grid=ultrafine) 6 1.420044000 0.432481000 0.947452000 6 1.557358000 1.011521000 0.815399000 6 2.636100000 1.544247000 0.155439000 1 2.770827000 2.614459000 0.047933000 6 3.622453000 0.709028000 0.459258000 6 2.457912000 1.242636000 0.356506000 6 2.253265000 2.624109000 0.457729000 8 0.39225800 0 0.967320000 1.474127000 6 0.389630000 2.486489000 0.180046000 6 1.535424000 1.684946000 0.389031000

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86 1 1.107742000 0.854033000 0.960576000 1 2.055016000 2.323121000 1.120350000 8 0.582910000 2.792267000 0.553244000 6 3.528806000 0.657188000 0.392822000 1 4.264970000 1.306828000 0.852159000 1 0.561284000 3.027047000 1.121499000 6 2.530944000 1.17471600 0 0.670260000 1 1.957700000 0.641831000 1.433889000 1 3.014114000 2.031070000 1.158909000 6 3.579548000 0.260987000 0.074491000 6 4.824543000 0.747024000 0.344145000 6 3.302853 000 1.103048000 0.099097000 1 5.058599000 1.801494000 0.210663000 1 2.340320000 1.490495000 0.229423000 6 5.769350000 0.103054000 0.922187000 6 4.243297000 1.955674000 0.67724700 0 1 6.731803000 0.292918000 1.236578000 1 4.012874000 3.011131000 0.800155000 6 5.480936000 1.457971000 1.091585000 1 6.215934000 2.122056000 1.538893000 1 1.770688000 3.023587 000 1.341930000 1 2.891576000 3.310801000 0.090239000 8 0.551292000 1.724468000 1.388735000 6 0.650020000 3.139609000 1.360409000 1 0.647876000 3.523267000 0.331195000 1 1.5586 47000 3.486904000 1.870074000 1 0.228773000 3.512552000 1.889262000 8 4.613781000 1.414639000 1.086880000 6 5.625049000 0.673800000 1.746598000 1 5.206804000 0.044858000 2.544280 000 1 6.180183000 0.037343000 1.043911000 1 6.303771000 1.409240000 2.182779000 3 SCF E(RB3LYP) = 574.617063687 au B3LYP/6 31G* opt 6 6.771574000 8.630894000 1.687862000 6 7.569073000 7.93110 2000 0.774979000 6 8.363353000 8.624495000 0.125107000 1 8.987143000 8.100390000 0.842120000 6 8.370677000 10.029157000 0.128435000 6 6.784044000 10.027263000 1.708808000 6 5.944 599000 10.752396000 2.739049000 8 5.994709000 7.903859000 2.561596000 6 4.973493000 8.679992000 3.168987000 8 5.465353000 9.856250000 3.741666000 6 7.583194000 10.724035000 0.79093 8000 1 7.586392000 11.809185000 0.818325000 1 4.559266000 8.069754000 3.971697000 1 6.536382000 11.504146000 3.270975000 1 5.095068000 11.272075000 2.263634000 8 9.183943000 10.614 353000 1.061563000 6 9.235959000 12.028931000 1.107813000 1 8.251689000 12.464178000 1.329542000 1 9.610484000 12.452456000 0.165636000 1 9.928734000 12.278653000 1.913758000 1 7.5 48908000 6.845817000 0.785689000 1 4.203203000 8.908037000 2.412216000 3* SCF E(RB3LYP) = 574.609623453 au B3LYP/6 31G(d) TD(Root=4,NStates=40) opt 6 0.915137000 0.818939000 0.017728000 6 0.037374000 1.921416000 0.045901000 6 1.359119000 1.665842000 0.089557000 1 2.094048000 2.460795000 0.078330000 6 1.804877000 0.318957000 0.043440000 6 0.479607000 0.541486000 0.024955000 6 1.490930000 1.636008000 0.006703000 8 2.238239000 1.106215000 0.057501000 6 3.114481000 0.012146000 0.317641000 8 2.774903000 1.135368000 0.406749000 6 0.925430000 0.791278000 0.031094000 1 1.291912000 1.808096000 0.039709000

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87 1 4.104065000 0.319581000 0.001992000 1 1.227645000 2.427778000 0.710065000 1 1.618873000 2.132484000 0.994247000 8 3.152485000 0.183947000 0.078455000 6 3.742159000 1.107137000 0.045024000 1 3.416422000 1.598750000 0.967909000 1 3.487910000 1.736061000 0.815864000 1 4.819665000 0.939287000 0.070637000 1 0.444747000 2.924232000 0.017941000 1 3.088346000 0.196727000 1.404729000 SCF E(RB3LYP) = 574.550443962 au B3LYP/6 31G* opt=(noeigentest,TS, calcall) 6 0.972665000 0.890417000 0.331878000 6 0.022083000 1.925563000 0.024779000 6 1.303026000 1.628851000 0.131363000 1 2.028936000 2.405104000 0.358238000 6 1.792094000 0.286330000 0.036372000 6 0.453748000 0.453183000 0.508516000 6 1.384254000 1.438531000 0.825457000 8 2.229810000 1.117761000 0.377489000 6 3.290383000 0.274316000 0.646712000 8 2.557280000 1.268000000 0.846544000 6 0.927022000 0.739261000 0.251847000 1 1.268320000 1.765065000 0.339843000 1 3.458387000 0.440260000 1.461537000 1 1.105610000 2.488131000 0.808037000 1 2.259553000 1.184777000 1.410005000 8 3.136804000 0.167988000 0.250883000 6 3.695900000 1.133638000 0.206238000 1 3.570957000 1.590796000 0.784964000 1 3.244843000 1.789909000 0.962866000 1 4.759942000 1.013486000 0.417561000 1 0.393643000 2.939391000 0.085372000 1 4.022980000 0.247986000 0.171472000 4 SCF E(RB3LYP) = 884.299542423 au B3LYP/6 31G* opt 6 7.160767000 8.305395000 2.046828000 6 8.229245000 7.724644000 1.351909000 6 9.089001000 8.519356000 0.609782000 1 9.922243000 8.086979000 0.065016000 6 8.893670000 9.908930000 0.546848000 6 6.965531000 9.686817000 2.005263000 6 5.820187000 10.281559000 2.789510000 8 6.343702000 7.472948000 2.776147000 6 5.102800000 8.052911000 3.194005000 6 4.063333000 7.989064000 2.069626000 1 4.429122000 8.532615000 1.190801000 1 3.161530000 8.507408000 2.418535000 8 5.286368000 9.342775000 3.723343000 6 7.833720000 10.486143000 1.247453000 1 7.670299000 11.559116000 1.226115000 1 4.785114000 7.439795000 4.041586000 6 3.718566000 6.542061000 1.665794000 1 4.637307000 6.038560000 1.345622000 1 3.354422000 6.000537000 2.549359000 6 2.680297000 6.479062000 0.565443000 6 1.312776000 6.427466000 0.866701000 6 3.063232000 6.504593000 0.782580000 1 0.996628000 6.399388000 1.907687000 1 4.121066000 6.537255000 1.035635000 6 0.354134000 6.404313000 0.147248000 6 2.108952000 6.482442000 1.800390000 1 0.701455000 6.359398000 0.108551000 1 2.427648000 6.498658000 2.839563000 6 0.749680000 6.432589000 1.485704000 1 0.0050890 00 6.411075000 2.277019000 1 6.157476000 11.129054000 3.395153000 1 5.027751000 10.653247000 2.119783000 8 9.795084000 10.599722000 0.218460000 6 9.651094000 12.005441000 0.311195000

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88 1 8.685896000 12.286310000 0.755070000 1 9.747506000 12.489055000 0.670720000 1 10.458348000 12.348888000 0.961040000 1 8.367670000 6.649302000 1.407396000 4* SCF E(RB3LYP) = 884.270488349 au B3LYP/6 31G(d) opt TD(root=12,nstates=12) 6 7.222386000 8.331566000 1.941024000 6 8.407705000 7.757298000 1.382678000 6 9.312351000 8.553511000 0.743617000 1 10.213910000 8.153709000 0.2 94943000 6 9.076846000 9.959095000 0.639827000 6 6.995391000 9.751751000 1.861509000 6 5.743500000 10.281023000 2.516045000 8 6.376628000 7.519768000 2.505574000 6 5.082818000 8 .084224000 3.065681000 6 3.986638000 7.917939000 2.038528000 1 4.259230000 8.367089000 1.076360000 1 3.129343000 8.485795000 2.421058000 8 5.343198000 9.370665000 3.532733000 6 7.915917000 10.540396000 1.214758000 1 7.752083000 11.609665000 1.150771000 1 4.939017000 7.466497000 3.951728000 6 3.537297000 6.462980000 1.767153000 1 4.423997000 5.862344000 1 .505102000 1 3.127927000 6.037727000 2.694663000 6 2.517644000 6.418565000 0.652794000 6 1.185848000 6.189585000 0.921528000 6 2.960137000 6.753086000 0.690920000 1 0.882298000 5.992282000 1.952765000 1 4.007496000 6.597547000 0.958877000 6 0.189873000 6.237979000 0.094288000 6 1.958364000 6.717346000 1.720008000 1 0.843815000 5.992624000 0.123728000 1 2.257912000 6.898538000 2.753302000 6 0.630561000 6.493019000 1.437050000 1 0.102422000 6.520897000 2.243314000 1 5.936578000 11.232329000 3.017878000 1 4.951995000 10.436369000 1.773411000 8 10.013722000 10.636566000 0.008433000 6 9.892324000 12.057692000 0.209865000 1 8.986225000 12.284349000 0.777150000 1 9.888935000 12.578097000 0.751605000 1 10.773344000 12.338583000 0.783388000 1 8.542600000 6.686378000 1.470207000 SCF E(RB3LYP) = 884.238637088 au B3LYP/6 31G* opt=(noeigentest,TS, calcall) 6 1.678847000 0.708297000 0.209546000 6 2.556165000 1.673167000 0.815357000 6 3.912498000 1.563707000 0.677649000 1 4.582916000 2.293885000 1.123045000 6 4.511520000 0.473566000 0.028950000 6 2.294662000 0.348842000 0.564715000 6 1.417996000 1.275546000 1.133490000 8 0.414115000 0.720340000 0.401616000 6 0.283697000 1.161748000 0.958286000 6 1.646353000 0.998014000 0.326233000 1 1.538345000 0.841711000 0.752806000 1 2.159278000 1.965299000 0.442814000 8 0.577609000 1.972463000 0.525294000 6 3.718039000 0.482265000 0.615717000 1 4.142522000 1.317799000 1.161935000 1 0.193787000 0.849194000 2.008872000 6 2.494414000 0.123470000 0.952941000 1 1.951743000 1.066372000 0.842064000 1 2.592829000 0.064670000 2.030684000 6 3.869176000 0.226994000 0.327749000 6 4.948106000 0.517052000 0.824135000 6 4.085922000 1.047542000 0.787813000 1 4.801446000 1.153647000 1.694700000 1 3.261126000 1.638267000 1.181129000

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89 6 6.206131000 0.447111000 0.223951000 6 5.341546000 1.120852000 1.392269000 1 7.0306240 00 1.029073000 0.628159000 1 5.489151000 1.767093000 2.253916000 6 6.406868000 0.372384000 0.888228000 1 7.386542000 0.431097000 1.355084000 1 1.796920000 2.193082000 1.573823000 1 0.451716000 0.942622000 1.487345000 8 5.878394000 0.503827000 0.047095000 6 6.549168000 0.556492000 0.705830000 1 6.291192000 0.593690000 1.773156000 1 6.314792000 1.5267280 00 0.247000000 1 7.616129000 0.352861000 0.598511000 1 2.107644000 2.482570000 1.382847000 5 SCF E(RB3LYP) = 460.096536748 au B3LYP/6 31G(d) opt 6 7.049476000 8.170845000 1.799912000 6 7.9759 44000 7.641839000 0.896761000 1 8.116951000 6.565947000 0.864474000 6 8.686636000 8.498692000 0.061276000 1 9.404326000 8.086692000 0.642920000 6 8.477163000 9.880291000 0.122664 000 1 9.030876000 10.548654000 0.530210000 6 6.840432000 9.554792000 1.889152000 6 5.863795000 10.083610000 2.917408000 8 6.364837000 7.292570000 2.602293000 6 5.225506000 7.8687 96000 3.229399000 8 5.518423000 9.074413000 3.867966000 6 7.560888000 10.396952000 1.036897000 1 7.407007000 11.472623000 1.101056000 1 4.904632000 7.158205000 3.991153000 1 6.30 5063000 10.899940000 3.497455000 1 4.949432000 10.471320000 2.436891000 1 4.438938000 8.009233000 2.468543000 5* SCF E(RB3LYP) = 460.089457266 au B3LYP/6 31G(d) TD(Root=5,NStates=40) opt 6 7.025388000 8.172629000 1.756428000 6 7.986378000 7.599506000 0.885249000 1 8.057785000 6.521220000 0.812577000 6 8.756478000 8.485808000 0.079141000 1 9.513288000 8.099152000 0.593797000 6 8.505481000 9.876741000 0.142506000 1 9.100277000 10.544062000 0.476688000 6 6.793370000 9.578381000 1.875219000 6 5.869782000 10.082104000 2.928825000 8 6.303436000 7.301790000 2.499921000 6 5.208098000 7.880233000 3.250061000 8 5.563711000 9.050071000 3.883124000 6 7.518015000 10.439754000 0.988850000 1 7.360674000 11.512520000 1.014796000 1 4.955855000 7.136306000 4.005862000 1 6.311727000 10.907006000 3.507012000 1 4.912898000 10.466741000 2.512424000 1 4.377683000 8.021391000 2.538661000 SCF E(RB3LYP) = 460.028626626 au B3LYP/6 31G* opt=(noeigentest,TS,verytight,calcall) 6 0.102079000 0.752860000 0.343424000 6 1.335249000 1.425357000 0.037819000 6 2.462929000 0.705793000 0.26432 5000 1 3.387956000 1.232146000 0.489463000 6 2.455073000 0.721162000 0.322185000 6 0.125831000 0.704895000 0.370158000 6 1.052329000 1.351563000 0.721806000 8 0.989469000 1.385 976000 0.525686000 6 2.568126000 0.513345000 0.476202000 8 2.228985000 0.636638000 0.819944000 6 1.304257000 1.405714000 0.038042000 1 1.280991000 2.492730000 0.069697000 1 2.5 48519000 1.325582000 1.213332000 1 1.147127000 2.427561000 0.607898000

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90 1 1.750604000 0.876456000 1.399431000 1 3.160732000 0.701017000 0.429418000 1 1.332025000 2.510882000 0.044 506000 1 3.363862000 1.251711000 0.589411000 6 SCF E(RB3LYP) = 769.779140373 au B3LYP/6 31G(d) opt 6 7.171354000 8.225351000 1.846507000 6 8.202882000 7.654343000 1.093608000 1 8.321079000 6 .575187000 1.106119000 6 9.047499000 8.473361000 0.350389000 1 9.847429000 8.027218000 0.234336000 6 8.868622000 9.860768000 0.352269000 1 9.527181000 10.500294000 0.228079000 6 6.987603000 9.614637000 1.871841000 6 5.881924000 10.185157000 2.727028000 8 6.372674000 7.376540000 2.568618000 6 5.162525000 7.950930000 3.083435000 6 4.062085000 7.940752000 2 .017232000 1 4.380210000 8.523908000 1.145201000 1 3.184099000 8.444747000 2.440033000 8 5.390564000 9.214230000 3.653116000 6 7.844354000 10.419158000 1.114332000 1 7.708532000 11.499056000 1.132249000 1 4.888348000 7.303632000 3.920541000 6 3.686841000 6.515285000 1.566109000 1 4.582826000 6.024596000 1.170464000 1 3.370562000 5.933238000 2.442258000 6 2.586919000 6.507424000 0.525506000 6 1.238895000 6.439757000 0.902242000 6 2.891769000 6.600498000 0.839325000 1 0.982751000 6.359456000 1.956931000 1 3.933313000 6.646956000 1.150963000 6 0.223526000 6.466235000 0.054789000 6 1.880457000 6.627982000 1.800376000 1 0.815694000 6.407651000 0.258700000 1 2.138799000 6.696106000 2.854078000 6 0.541502000 6.561299000 1.410681000 1 0.247443000 6.578486000 2.157881000 1 6.249884000 11.010710000 3.344461000 1 5.058993000 10.579856000 2.110022000 6 SCF E(RB3LYP) = 769.759522462 au B3LYP/6 31G(d) TD(Ro ot=14,NStates=40) opt 6 7.234396000 8.232797000 1.849140000 6 8.378811000 7.824242000 1.152339000 1 8.631353000 6.770736000 1.136372000 6 9.211430000 8.775372000 0.461956000 1 10.066 667000 8.399913000 0.088292000 6 8.919280000 10.129600000 0.480318000 1 9.530253000 10.845709000 0.053727000 6 6.962722000 9.609706000 1.914285000 6 5.816245000 10.061397000 2.76179 6000 8 6.488303000 7.316447000 2.452565000 6 5.190906000 7.789724000 2.993605000 6 4.124359000 7.768843000 1.920870000 1 4.439093000 8.340730000 1.038457000 1 3.245929000 8.283 508000 2.326703000 8 5.405048000 9.034541000 3.630593000 6 7.793991000 10.539947000 1.195305000 1 7.520713000 11.590427000 1.224156000 1 4.988467000 7.086737000 3.799755000 6 3.6 94675000 6.357121000 1.457725000 1 4.556679000 5.838191000 1.018301000 1 3.407505000 5.787545000 2.361395000 6 2.555677000 6.422986000 0.471531000 6 1.277642000 6.954866000 0.916 553000 6 2.741722000 6.073867000 0.851740000 1 1.039733000 6.977756000 1.980136000 1 3.721664000 5.702872000 1.163248000 6 0.229603000 7.017332000 0.052773000 6 1.716123000 6.2 04735000 1.824407000

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91 1 0.756109000 7.363018000 0.262035000 1 1.863590000 5.859466000 2.842111000 6 0.430969000 6.678002000 1.373300000 1 0.385403000 6.779520000 2.087165000 1 6 .111412000 10.910761000 3.390600000 1 4.999416000 10.416391000 2.108977000 SCF E(RB3LYP) = 769.716873676 au B3LYP/6 31G* opt=(noeigentest,TS,calcall) 6 2.477072000 0.657715000 0.136409000 6 3.389 458000 1.570735000 0.767273000 6 4.741324000 1.457249000 0.559763000 1 5.416662000 2.162628000 1.039196000 6 5.294521000 0.419205000 0.247260000 6 3.045704000 0.346548000 0.74887 6000 6 2.144363000 1.207550000 1.374002000 8 1.224163000 0.663747000 0.379586000 6 0.512331000 1.289500000 0.788457000 6 0.863969000 1.045912000 0.216041000 1 0.786198000 0.786 024000 0.845247000 1 1.386589000 2.014543000 0.253319000 8 1.354163000 2.054040000 0.254674000 6 4.462406000 0.479431000 0.862757000 1 4.866213000 1.275360000 1.484652000 1 0.6 40852000 1.068173000 1.858486000 6 1.676185000 0.017852000 0.976666000 1 1.120319000 0.959019000 0.948002000 1 1.750060000 0.278897000 2.031835000 6 3.064262000 0.205483000 0.402 358000 6 4.132227000 0.605176000 0.810856000 6 3.305430000 1.176894000 0.578704000 1 3.967083000 1.359089000 1.578345000 1 2.489486000 1.820267000 0.901261000 6 5.402991000 0.4 53734000 0.254562000 6 4.574318000 1.332613000 1.138515000 1 6.218505000 1.089987000 0.589119000 1 4.740812000 2.095552000 1.894834000 6 5.628152000 0.516396000 0.723929000 1 6 .617970000 0.638631000 1.155732000 1 2.500741000 2.083625000 1.907794000 1 1.165596000 0.843659000 1.655916000 1 2.971179000 2.338404000 1.411084000 1 6.371295000 0.349457000 0.3 68086000 9 SCF E(RB3LYP) = 1191.53950741 au B3LYP/6 31G(d) opt 6 10.783585000 18.582064000 3.454089000 6 8.576035000 19.470596000 3.756137000 6 8.234706000 18.057467000 3.152996000 6 9.109163000 1 6.972650000 3.782833000 1 10.719795000 18.926574000 2.409316000 1 11.798912000 18.733596000 3.828520000 1 7.187483000 17.800614000 3.330063000 1 8.401531000 18.050783000 2.072629000 8 9.930017000 19.344379000 4.268558000 8 10.497133000 17.200763000 3.538800000 6 10.476150000 23.871235000 2.165489000 6 9.604324000 22.759995000 1.938956000 6 8.954819000 22.618635000 0.712838000 6 9.381050000 21.784511000 2.984874000 6 8.549844000 20.651204000 2.731415000 6 7.758885000 20.637094000 1.546484000 6 8.006293000 21.618968000 0.507346000 6 11.065027000 24.070262000 3.382517000 6 10.002030000 22.059780000 4.252162000 6 6.658828000 19.742026000 1.303863000 6 7.264469000 21.575488000 0.715431000 6 6.263499000 20.665736000 0.910656000 6 5.941999000 19.758014000 0.135170000 1 6.338940000 19.066830000 2.083066000 1 7.504026000 22.310632000 1.480107000 1 5.698128000 20.651122000 1.838117000

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92 1 5.106032000 19.074163000 0.013501000 6 10.798037000 23.159686000 4.441670000 1 10.638487000 24.567407000 1.346022000 1 11.715133000 24.924524000 3.550612000 1 9.819958000 21.400408000 5.086561000 1 11.227686000 23.341795000 5.423219000 6 7.687590000 19.739316000 4.983164000 6 6.455689000 20.394178000 4.825477000 6 8.063520000 19.281503000 6.249671000 6 5.607414000 20.577124000 5.921934000 6 7.208806000 19.471737000 7.341204000 6 5.985155000 20.109291000 7.188812000 1 9.025433000 18.802893000 6.384248000 1 7.508937000 19.118196000 8.324278000 1 5.313084000 20.267490000 8.026314000 1 8.870524000 15.998691000 3.343282000 1 9.156264000 23.332935000 0.082817000 1 8.921905000 16.909162000 4.863241000 1 6.176185000 20.775852000 3.851978000 8 4.396385000 21.205640000 5.860641000 6 3.973459000 21.734996000 4.613945000 1 4.667203000 22.501207000 4.243912000 1 3.869482000 20.949433000 3.853693000 1 2.998081000 22.189273000 4.798161000 9 SCF E(RB3LYP) = 1191.53950741 au B3LYP/6 31G(d) TD(NStates=80) 6 0.157460000 2.708616000 1.942379000 6 0.568764000 0.693743000 0.862155000 6 0.756446000 0.291449000 2.372172000 6 1.388344000 1.436394000 3.164638000 1 1.145081000 2.231218000 2.047269000 1 0.285678000 3.770855000 1.720439000 1 1.400041000 0.586760000 2.464574000 1 0.207269000 0.047863000 2.827131000 8 0.539807000 2.146647000 0.860218000 8 0.572354000 2.607694000 3.148368000 6 3.231744000 1.441124000 2.378798000 6 2.650489000 0.658278000 1.332115000 6 3.376076000 0.380847000 0.749921000 6 1.302293000 0.931302000 0.881350000 6 0.749994000 0.178198000 0.199081000 6 1.438854000 0.988735000 0.639098000 6 2.792985000 1.237560000 0.181374000 6 2.514037000 2.415305000 3.013946000 6 0.585024000 1.946377000 1.604230000 6 0.871729000 2.009282000 1.479925000 6 3.520216000 2.370204000 0.666791000 6 2.944757000 3.280252000 1.508434000 6 1.586836000 3.104582000 1.890879000 1 0.169708000 1.952791000 1.758480000 1 4.543293000 2.501363000 0.322315000 1 3.502669000 4.143615000 1.859690000 1 1.101941000 3.856648000 2.507782000 6 1.164280000 2.646559000 2.630652000 1 4.256125000 1.222108000 2.670707000 1 2.958393000 2.996293000 3.817474000 1 0.444561000 2.149120000 1.353246000 1 0.577068000 3.388306000 3.165623000 6 1.821308000 0.299097000 0.060576000 6 1.890161000 0.960881000 0.555058000 6 2.922542000 1.157738000 0.009956000 6 3.052648000 1.358308000 1.222841000 6 4.080416000 0.751842000 0.682820000 6 4.157513000 0.496893000 1.284266000 1 2.865291000 2.142654000 0.436271000 1 4.931353000 1.425855000 0.738668000 1 5.047136000 0.824546000 1.812782000 1 1.499015000 1.147195000 4.214812000 1 4.402448000 0.556665000 1.065390000 1 2.387776000 1.667844000 2.772279000

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93 1 1.028263000 1.614994000 0.527361000 8 3.2048260 00 2.560907000 1.852109000 6 2.109235000 3.462561000 1.857980000 1 1.233484000 3.031244000 2.360285000 1 1.825880000 3.763638000 0.840647000 1 2.447943000 4.340011000 2.412078000 10 SCF E(RB3LYP) = 1191.55577998 au B3LYP/6 31G(d) opt 6 9.466303000 16.825587000 2.466827000 6 9.005180000 19.110590000 2.970394000 6 7.639236000 18.498510000 3.331337000 6 7.856044000 17.1 96331000 4.155492000 1 8.650606000 16.488978000 1.800247000 1 10.364397000 16.238034000 2.264377000 1 7.055151000 19.218977000 3.910895000 1 7.075416000 18.290735000 2.415925000 8 9 .791773000 18.176537000 2.201506000 8 9.114475000 16.598825000 3.804925000 6 9.171450000 24.127381000 3.132782000 6 8.980908000 22.930034000 2.374551000 6 8.694963000 22.994646000 1.0 10516000 6 9.075527000 21.639457000 3.024243000 6 8.901188000 20.453684000 2.258947000 6 8.580558000 20.542691000 0.878511000 6 8.480066000 21.843690000 0.251563000 6 9.425181000 24 .084363000 4.475619000 6 9.331027000 21.654163000 4.438773000 6 8.329760000 19.404779000 0.038882000 6 8.151299000 21.942575000 1.137048000 6 7.913394000 20.826637000 1.890140000 6 8.003176000 19.542210000 1.285065000 1 8.423157000 18.414411000 0.457468000 1 8.089447000 22.934828000 1.577890000 1 7.659965000 20.913576000 2.943166000 1 7.818230000 18.655118000 1 .885327000 6 9.497720000 22.825079000 5.132312000 1 9.102350000 25.078585000 2.610147000 1 9.565468000 25.000535000 5.042495000 1 9.378430000 20.727414000 4.997285000 1 9.685793000 22.789531000 6.202027000 6 7.847879000 17.448691000 5.652946000 6 6.609875000 17.604713000 6.296946000 6 9.030428000 17.570230000 6.382859000 6 6.559848000 17.892145000 7.663408000 6 8.970756000 17.855623000 7.752572000 6 7.751205000 18.019721000 8.394841000 1 9.981980000 17.420229000 5.886810000 1 9.891315000 17.946254000 8.323327000 1 7.688477000 18.237890000 9.456278000 1 7.052342000 16.483234000 3.912273000 1 8.624945000 23.968060000 0.529128000 1 9.551064000 19.254474000 3.904292000 1 5.695844000 17.494767000 5.721973000 8 5.408381000 18.060244000 8.378585000 6 4.169394000 17.948415000 7.698271000 1 4.076097000 18.698029000 6.900957000 1 4.032100000 16.947162000 7.268257000 1 3.397961000 18.125307000 8.450058000 10 SCF E(RB3LYP) = 1191.55577998 au B3LYP/6 31G(d) TD(NStates=80) 6 0.118323000 2.948052000 1.523599000 6 0.455952000 0.763669000 0.758007000 6 0.440716000 1.206918000 0.412566000 6 1.721358000 1.892419000 0.145959000 1 0.109146000 3.634645000 0.687032000 1 0.035600000 3.489520000 2.468452000 1 0.711714000 0.337250000 1.017838000 1 0.114560000 1.890367000 1.063418000 8 0.828505000 1.897872000 1.568661000 8 1.439810000 2.491024000 1.421091000

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94 6 2.772334000 3.640975000 0.082955000 6 2.797784000 2.214302000 0.010941000 6 3.925323000 1.558057000 0.505440000 6 1.644466000 1.441455000 0.400406000 6 1.684996000 0.022336000 0.319236000 6 2.830726000 0.623799000 0.215686000 6 3.968487000 0.169090000 0.631123000 6 1.666242000 4.302675000 0.539196000 6 0.505709000 2.189186000 0.859233000 6 2.940921000 2.045049000 0.390687000 6 5.124162000 0.473296000 1.176891000 6 5.174258000 1.830896000 1.330107000 6 4.060743000 2.621409000 0.931230000 1 2.128282000 2.677098000 0.066806000 1 5.963422000 0.151415000 1.473728000 1 6.055513000 2.308070000 1.750038000 1 4.102832000 3.701114000 1.049205000 6 0.517293000 3.558640000 0.924726000 1 3.659690000 4.188464000 0.226183000 1 1.656869000 5.387181000 0.603680000 1 0.405009000 1.679286000 1.148441000 1 0.3674810 00 4.083626000 1.274710000 6 2.872935000 0.917845000 0.319737000 6 3.612035000 0.548443000 0.815607000 6 3.178585000 0.357056000 1.559922000 6 4.644527000 0.386854000 0.708296000 6 4.216905000 0.577429000 1.658682000 6 4.946655000 0.954247000 0.539657000 1 2.624101000 0.667364000 2.437573000 1 4.458926000 1.011850000 2.625175000 1 5.756289000 1.6746310 00 0.600651000 1 2.032252000 2.687192000 0.550661000 1 4.788165000 2.145449000 0.813086000 1 0.149694000 0.127065000 1.405144000 1 3.374333000 1.001116000 1.773062000 8 5.41954 2000 0.809025000 1.750762000 6 5.163519000 0.277557000 3.040109000 1 4.145343000 0.510968000 3.379477000 1 5.310720000 0.810517000 3.066502000 1 5.883265000 0.753691000 3.7085750 00 11 SCF E(RB3LYP) = 1383.27327750 au (not fully converged) B3LYP/6 31G(d) opt 6 2.357400000 3.222642000 2.645247000 6 2.077940000 3.692021000 1.365152000 6 1.928769000 1.947031000 3.004474000 1 2.398774000 4.692074000 1.080623000 1 2.129558000 1.555114000 3.997844000 6 1.387171000 2.915824000 0.423814000 6 1.241612000 1.163444000 2.079711000 1 0.930543000 0.167263000 2. 372275000 6 0.955968000 1.618782000 0.782898000 1 2.894932000 3.848412000 3.352501000 6 1.172982000 3.537586000 0.945333000 6 0.181904000 0.675609000 0.175304000 8 0.108673000 3.261372000 1.491603000 8 0.511486000 0.994279000 1.559789000 6 0.141597000 2.059148000 2.209034000 1 1.960966000 3.220839000 1.647261000 1 1.200191000 1.856653000 2.394928000 1 0.404229000 2.141991000 3.160695000 6 2.872883000 0.224555000 1.196036000 6 1.927736000 1.161499000 0.653178000 6 0.705324000 0.796149000 0.011110000 6 2.300552000 2.557392000 0.743623000 6 1.501842000 3.526354000 0.138507000 6 0.405590000 3.173916000 0.645021000 6 0.010990000 1.781841000 0.750387000 6 4.028786000 0.629760000 1.810591000 6 3.493988000 2.942870000 1.432406000

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95 1 1.770634000 4.576163000 0.236616000 6 0.311757000 4.184010000 1.361317000 6 1.045835000 1.506300000 1.687173000 6 1.679584000 2.497958000 2.389950000 6 1.333129000 3.864881000 2.210608000 1 0.000797000 5.217256000 1.229374000 1 1.338082000 0.484691000 1.877296000 1 2.457250000 2.230436000 3.100510000 1 1.860924000 4.638542000 2.761422000 6 4.340078000 2.008995000 1.960165000 1 2.682193000 0.831738000 1.095345000 1 4.723094000 0.118378000 2.184462000 1 3.720973000 4.004181000 1.501679000 1 5.251768000 2.310032000 2.469046000 1 1.235991000 4.626599000 0.856471000 6 1.350792000 0.806494000 0.049958000 6 2.149240000 0.013220000 0.851206000 6 1.964932000 1.772811000 0.757805000 6 3.544124000 0.098023000 0.831344000 6 3.354343000 1.877066000 0.780262000 6 4.157555000 1.046962000 0.004034000 1 1.702724000 0.760624000 1.498422000 1 1.364642000 2.438202000 1.366460000 1 3.825331000 2.623961000 1.414015000 1 5.236071000 1.149640000 0.030811000 8 4.213832000 0.763801000 1.653230000 6 5.630270000 0.706778000 1.674634000 1 6.059639000 0.927222000 0.688036000 1 5.991884000 0.273709000 2.012717000 1 5.949705000 1.472001000 2.384627000 11* SCF E(RB3LYP) = 1383.27326853 au B3LYP/6 31G(d) TD(NStates=80) 6 2.363609000 3.216808000 2.647224000 6 2.086372000 3.687627000 1.367066000 6 1.930100000 1.942750000 3.005812000 1 2.410702000 4.686683000 1.082917000 1 2.128701000 1.549851000 3.999281000 6 1.393430000 2.914011000 0.425187000 6 1.241415000 1.161640000 2.080240000 1 0.926188000 0.166667000 2.372381000 6 0.958497000 1.617964000 0.783145000 1 2.902470000 3.840671000 3.355207000 6 1.180264000 3.537386000 0.943804000 6 0.182573000 0.676285000 0.175816000 8 0.101955000 3.263194000 1.490079000 8 0.513108000 0.995026000 1.560739000 6 0.137982000 2.061223000 2.208758000 1 1.968023000 3.220198000 1.645989000 1 1.197461000 1.861985000 2.394408000 1 0.407371000 2.144379000 3.160751000 6 2.870126000 0.229878000 1.200296000 6 1.923720000 1.164929000 0.656583000 6 0.702275000 0.796840000 0.013633000 6 2.294531000 2.561430000 0.745576000 6 1.494408000 3.528616000 0.139654000 6 0.399713000 3.173785000 0.644957000 6 0.007626000 1.780871000 0.750272000 6 4.025867000 0.637279000 1.813714000 6 3.488104000 2.949203000 1.432784000 1 1.761030000 4.579005000 0.237985000 6 0.317382000 4.182023000 1.364063000 6 1.045948000 1.502793000 1.690213000 6 1.678577000 2.492731000 2.396250000 6 1.335036000 3.860375000 2.216774000 1 0.007102000 5.215980000 1.232009000 1 1.3360080 00 0.480386000 1.879429000 1 2.452923000 2.223454000 3.109820000 1 1.862333000 4.632715000 2.769995000 6 4.335779000 2.016902000 1.961064000 1 2.680352000 0.826619000 1.100922000

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96 1 4.721241000 0.109552000 2.188345000 1 3.714296000 4.010838000 1.500086000 1 5.247907000 2.319594000 2.468228000 1 1.245093000 4.626345000 0.853936000 6 1.350015000 0.8098180 00 0.052611000 6 2.149590000 0.009603000 0.852714000 6 1.963021000 1.778950000 0.753293000 6 3.544705000 0.102600000 0.832268000 6 3.351966000 1.885683000 0.774515000 6 4.15643 6000 1.054743000 0.007756000 1 1.704318000 0.758613000 1.498892000 1 1.361537000 2.444395000 1.360604000 1 3.822214000 2.635120000 1.405942000 1 5.234584000 1.161985000 0.0246980 00 8 4.214802000 0.763409000 1.649608000 6 5.631352000 0.707380000 1.672250000 1 6.061065000 0.907722000 0.681657000 1 5.993113000 0.266053000 2.030128000 1 5.949909000 1.48779 8000 2.365916000 12 SCF E(RB3LYP) = 1383.29751043 au B3LYP/6 31G(d) opt 6 1.408324000 1.001067000 3.104307000 6 2.026751000 1.045487000 1.855372000 6 0.090103000 0.566835000 3.200791000 1 3. 058278000 1.374552000 1.787308000 1 0.408139000 0.516095000 4.165195000 6 1.355464000 0.669096000 0.684713000 6 0.597514000 0.201980000 2.044255000 1 1.628839000 0.126155000 2.12 1391000 6 0.003766000 0.255561000 0.780648000 1 1.960158000 1.299203000 3.991789000 6 2.097149000 0.765535000 0.659423000 6 0.800587000 0.200504000 0.446747000 8 1.683225000 0. 297952000 1.539310000 8 0.465329000 0.596832000 1.603555000 6 0.590998000 0.049488000 2.346274000 1 1.840927000 1.726697000 1.127847000 1 0.487872000 1.222452000 0.672070000 1 0.299859000 0.881754000 2.852677000 1 0.851824000 0.820271000 3.085197000 6 2.364348000 2.323346000 0.304795000 6 3.017967000 1.047351000 0.258321000 6 2.317833000 0.186047000 0. 283997000 6 4.460806000 1.049048000 0.171754000 6 5.147197000 0.165696000 0.109218000 6 4.474911000 1.388428000 0.100829000 6 3.027858000 1.409570000 0.177049000 6 3.077632000 3.493209000 0.269049000 6 5.167351000 2.292014000 0.148203000 1 6.234037000 0.158600000 0.054760000 6 5.200565000 2.617914000 0.012571000 6 2.402499000 2.702017000 0.121821000 6 3.133738000 3.857242000 0.027547000 6 4.555379000 3.822874000 0.020562000 1 6.285921000 2.567604000 0.033583000 1 1.322005000 2.784211000 0.132684000 1 2.620268000 4.814064000 0.015797000 1 5.117397000 4.749993000 0.090389000 6 4.498730000 3.484377000 0.193700000 1 1.286308000 2.359069000 0.378044000 1 2.551012000 4.443357000 0.300669000 1 6.252838000 2.264135000 0.088204000 1 5.044608000 4.423704000 0.171392000 6 3.609773000 0.688024000 0.549816000 6 4.221484000 0.540763000 0.258187000 6 4.392658000 1.825662000 0.741744000 6 5.612304000 0.622694000 0.163757000 6 5.786581000 1.738949000 0.637090000 6 6.398276000 0.526562000 0.351357000 1 3.597109000 1.415728000 0.125023000

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97 1 3.921355000 2.777402000 0.973224000 1 6.396732000 2.625730000 0.786640000 1 7.477077000 0.436974000 0.270878000 8 6.303092000 1.768891000 0.107662000 6 5.566112000 2.964511000 0.309311000 1 4.984033000 3.235363000 0.581357000 1 4.888576000 2.881181000 1.169353000 1 6.306449000 3.741959000 0.507214000 12* SCF E(RB3LYP) = 1383.29751043 au B3LYP/6 31G(d) TD(NStates=80) 6 1.408324000 1.001067000 3.104307000 6 2.026751000 1.045487000 1.855372000 6 0.090103000 0.566835000 3.200791000 1 3.058278000 1.374552000 1.787308000 1 0.408139000 0.516095000 4.165195000 6 1.355464000 0.669096000 0.684713000 6 0.597514000 0.201980000 2.044255000 1 1.628839000 0.126155000 2.121391000 6 0.003766000 0.255561000 0.780648000 1 1.960158000 1.299203000 3.991789000 6 2.097149000 0.765535000 0.659423000 6 0.800587000 0.200504000 0.446747000 8 1.683225000 0.297952000 1.539310000 8 0.465329000 0.596832000 1.603555000 6 0.590998000 0.049488000 2.346274000 1 1.840927000 1.726697000 1.127847000 1 0.487872000 1.222452000 0.672070000 1 0.299859000 0.881754000 2.852677000 1 0.851824000 0.820271000 3.085197000 6 2.364348000 2.323346000 0.304795000 6 3.017967000 1.047351000 0.258321000 6 2.317833000 0.186047000 0.283997000 6 4.460806000 1.049048000 0.171754000 6 5.147197000 0.165696000 0.109218000 6 4.474911000 1.388428000 0.100829000 6 3.027858000 1.409570000 0.177049000 6 3.077632000 3.493209000 0.269049000 6 5.167351000 2.292014000 0.148203000 1 6.234037000 0.158600000 0.054760000 6 5.200565000 2.617914000 0.012571000 6 2.402499000 2.702017000 0.121821000 6 3.133738000 3.857242000 0.027547000 6 4.555379000 3.822874000 0.020562000 1 6.285921000 2.567604000 0.033583000 1 1.322005000 2.784211000 0.132684000 1 2.620268000 4.814064000 0.015797000 1 5.117397000 4.749993000 0.090389000 6 4.498730000 3.484377000 0.193700000 1 1.286308000 2.359069000 0.378044000 1 2.551012000 4.443357000 0.300669000 1 6.252838000 2.264135000 0.088204000 1 5.044608000 4.423704000 0.171392000 6 3.609773000 0.688024000 0.549816000 6 4.221484000 0.540763000 0.258187000 6 4.392658000 1.825662000 0.741744000 6 5.612304000 0.622694000 0.163757000 6 5.786581000 1.738949000 0.637090000 6 6.3982760 00 0.526562000 0.351357000 1 3.597109000 1.415728000 0.125023000 1 3.921355000 2.777402000 0.973224000 1 6.396732000 2.625730000 0.786640000 1 7.477077000 0.436974000 0.270878000 8 6.303092000 1.768891000 0.107662000 6 5.566112000 2.964511000 0.309311000 1 4.984033000 3.235363000 0.581357000 1 4.888576000 2.881181000 1.169353000 1 6.306449000 3.7419590 00 0.507214000