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QUANTUM CHEMICAL STUDY ON ATMOSPHERICALLY IMPORTANT WATER COMPLEXES: A GAUSSIAN APPROACH

QUANTUM CHEMICAL STUDY ON ATMOSPHERICALLY IMPORTANT WATER COMPLEXES: A GAUSSIAN APPROACH

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Sections

  • 1.2 Overview of the study
  • 2.1. Fundamental Interactions
  • 2.1.1. Noncovalent Intermolecular Interactions
  • Table 2.1 Fundamental Interaction10
  • 2.2. Computational Chemistry
  • Table 2.2 Theoretical Methods in Computational Chemistry10
  • 2.2.3. Types of Calculations
  • 2.2.4. Terminology
  • 2.2.5.1 Supermolecular Approach
  • 2.2.7 The Water Complexes
  • 3.1 Overview of the Study
  • 3.2 Carbon dioxide Experiment
  • 3.3 Nitrogen Experiment
  • Methodology
  • 4.2 Computational Methods
  • Results and Discussion
  • Complexes
  • Table 5.1 Details of Structure I of H2O-N2
  • Figure 5.2 Structure II of H2O-N2
  • Figure 5.3 Structure III of H2O-N2
  • Table 5.3 Details of Structure III of H2O-N2
  • Table 5.4 Details of Structure IV of H2O-N2
  • Figure 5.5 Structure V of H2O-N2
  • Figure 5.6 Structure VI of H2O-N2
  • Table 5.6 Details of Structure VI of H2O-N2
  • Table 5.7 Calculated Energy of Water-Nitrogen complexes by different methods
  • Figure 5.7 Energy vs. Distance diagram of Water Nitrogen complex
  • Figure 5.9 Structure I of H2O-CO2
  • Figure 5.10 Structure II of H2O-CO2
  • Table 5.10 Details of Structure II of H2O-CO2
  • Table 5.11 Details of Structure III of H2O-CO2
  • Figure 5.12 Structure IV of H2O-CO2
  • Figure 5.13 Structure V of H2O-CO2
  • Table 5.13 Details of Structure V of H2O-CO2
  • Method
  • Distance
  • 5.1.3 Vibrational Frequencies Calculation
  • Table 5.16 Details of Structure I of H2O-N2
  • Figure 5.22 Structure III of two water-nitrogen complex
  • Figure 5.25 Structure I of two water-carbon dioxide complex
  • Figure 5.26 Structure II of two water-carbon dioxide complex
  • 5.2 Molecular Orbital Interaction from Gaussian
  • Figure 5.29 Molecular orbital interaction between one water -nitrogen complex
  • 5.3 Comparison of IR absorption for nitrogen and Water-nitrogen complex:
  • 5.4 Summery of the Results
  • Table 5.25 Summery of the Results
  • Conclusion and Future Works
  • References
  • Appendix A
  • Appendix B

QUANTUM CHEMICAL STUDY ON ATMOSPHERICALLY IMPORTANT WATER

COMPLEXES: A GAUSSIAN APPROACH





A Thesis
Presented to
The Faculty of the College of Graduate Studies
Lamar University







In Partial Fulfillment
of the Requirements for the Degree
Master of Engineering Science
by
Shakib Bin Reza
July 2012


QUANTUM CHEMICAL STUDY ON ATMOSPHERICALLY IMPORTANT WATER
COMPLEXES: A GAUSSIAN APPROACH
SHAKIB BIN REZA
Approved:


__________________________________
Qin Qian
Supervising Professor


__________________________________
Jewel Andrew Gomes
Co-Supervisor



__________________________________
C. Jerry Lin
Committee Member


____________________________________
Robert Yuan
Chair, Department of Civil Engineering


____________________________________
Jack R. Hopper
Dean, College of Engineering


____________________________________
Victor A. Zaloom
Dean, College of Graduate Studies



© 2012 by Shakib Bin Reza
No part of this work can be reproduced without permission except as indicated by the
“Fair Use” clause of the copyright law. Passages, images, or ideas taken from this work
must be properly credited in any written or published materials.























ABSTRACT
QUANTUM CHEMICAL STUDY ON ATMOSPHERICALLY IMPORTANT WATER
COMPLEXES: A GAUSSIAN APPROACH
by
Shakib Bin Reza

Water vapors are widespread in the atmosphere. They readily form hydrogen
bonds and makes complexes with themselves and other acids with bond energies in
between 5 kcal/mol to 12 kcal/mol. Much weaker van der Waals complexes with bond
energies of about 1 kcal/mol can also be formed with other constituents of the
atmosphere, such as O
2
, N
2
, CO
2
, and so forth. Although to date only the presence of O
2
-
O
2
intermolecular complexes in the atmosphere were identified, the presence of other
atmospherically relevant hydrated complexes are very likely, since their bonding energies
are higher than the O
2
-O
2
complexes. Using statistical mechanics, the abundance of these
complexes were estimated and found significant at the ground level. Water itself absorbs
radiation in the IR and near-IR, and is considered as a significant contributor to the
greenhouse effect. If formation of additional IR active frequencies can be found in the
above hydrated complexes, then these new frequencies can contribute to the estimated
greenhouse effect that is not currently considered for making the estimate.
In this study, these concerns were highlighted with theoretical quantum chemical
calculations. The objectives were to prove the formation of H
2
O-N
2
and H
2
O-CO
2
Complexes using Gaussian simulation program, to determine the single point energy of
these complexes, to find out the optimized structure and to calculate the vibrational
ii

frequencies. To compare the calculated results with the results obtained from laboratory
experiment was another goal of this study.
Quantum chemical simulations of these hydrated complexes have been performed
at various degrees of theories, and basis sets which confirmed the formation of the
complexes at certain conditions. The intermolecular potential energy surfaces for these
complexes have been calculated using a combination of Mөller-Plesset perturbation
theory and Density Functional theory. The results obtained from theoretical studies of the
water–nitrogen complex correlates satisfactorily with the experimental data. For one
water-nitrogen complex we obtained a geometry which has a point group of C
s
, E
h
=-
186.03(E
h
=627.509 kcal/mol) and vibrational peak at 737.80 cm
-1
, 1658.54 cm
-1
and
2006.1 cm
-1
. While for one water-carbon dioxide complex we obtained a C
1
point group
geometry with E
h
=-265.11 and vibrational peak at 1647.81 cm
-1
and 3864.9 cm
-1
.Two
molecules of water have been introduced in the complex formation to find out the
solvation effect and minimization of energies in the complexes. For two water-nitrogen
complex we obtained a geometry which has a point group of C
s
, E
h
= -262.48 and
vibrational peak at 1671.93 cm
-1
and 3839.61 cm
-1
. We obtained a C
s
point group with
E
h=
-341.56 for two water-carbon dioxide complex which has frequency peak at 1630.29
cm
-1
and 2402.28 cm
-1
. Graphical views of the Molecular orbitals were also produced to
explain the overlapping of the orbitals, and electronic distributions in the complexes. It is
expected that the results from this study will provide new insights into the role of van der
Waals complexes in the atmosphere and will be included in climate models. The obtained
frequencies can be used to identify these complexes in the atmosphere and interstellar
spaces. The work concludes with a forward look to work on larger molecules.
iii


ACKNOWLEDGEMENTS

All the praise is due to Allah, the Most Beneficent and the Most Merciful, for
blessing me with the ability to pursue my graduate studies.
I am deeply indebted to my co-supervisor Dr. Andrew Jewel Gomes for all his
guidance throughout this research. The visions for the current project, the context of the
research, and the content of this thesis, in large part, have been possible because of him.
He has never failed to pepper our conversations with words of encouragement and
provide a listening ear whenever I needed one despite his hectic schedules. His way of
guidance has been an important key factor that motivates me to learn a lot of knowledge
through this research, and I hope this lesson will prevail for the rest of my life.
I would like to extend my appreciation to the committee members, Dr. Qin Qian
and Dr. C. Jerry Lin, for serving in my Graduate committee.
Special thanks go to Dr. Mien Jao, who guided me ceaselessly since the very
beginning I am at this University.


iv

TABLE OF CONTENTS

LIST OF TABLES …....................................................................................................vii
LIST OF FIGURES ….....................................................................................................ix
Chapter
1. Introduction……………………………………………………………………..............1
1.1 Atmospheric Complexes……………….......…….…………………………….……1
1.2 Overview of the study…...........................................................................................2
2. Literature Review ……………………………………………..……….……….……....4
2.1 Fundamental Interactions…......................................................................................4
2.1.1 Nonvalent Intermolecular Interactions…..........................................................4
2.2 Computational Chemistry….....................................................................................6
2.2.1. Ab Initio Methods…………………………………………..……………...….7
2.2.1.1. Hartree - Fock Method (HF)………………….…..……………..........….8
2.2.1.2. Post – Hartree Fock Methods……………………………………….……9
2.2.1.3. Basis Set………………………………………………….….…….……..9
2.2.2. Density Functions Theory (DFT)….................................................................12
2.2.3. Types of Calculations…...................................................................................13
2.2.4. Terminology…..................................................................................................13
2.2.5. Intermolecular Interaction Energy Calculation…………………….….......…14
2.2.5.1. Supermolecular Approach…....................................................................14

v

2.2.5.2. Effective ab initio methods for Supermolecular Approach…..................15
2.2.6. The Water Complexes….................................................................................15
3. Previous works…………………………………………………………………….…..17
3.1 Overview of the Study....................................................................................…....17
3.2 Carbon dioxide Experiment............................................................................…....18
3.3 Nitrogen Experiment...................................................................................…........18
4. Methodology......................................................................................................…........20
4.1 Instruments………………………………………………………….....……….…20
4.2 Computational Methods…......................................................................................20
4.2.1 Geometry Optimization and Vibrational Frequency calculations….................20
4.3 Computational Details…………………………………………….........................20
5. Results and Discussion…...............................................................................................22
5.1 Geometry Optimization and Vibrational Frequency Calculations for
Water Complexes...................................................................................….............22
5.1.1 Geometry Optimization Calculation of one Water Nitrogen
Complexes........................................................................................................22
5.1.2 Geometry Optimization Calculation of one Water Carbon dioxide
Complexes…....................................................................................................29
5.1.3 Vibrational Frequencies Calculation....................................................….........35
5.1.4 Geometry Optimization Calculation of two Water Nitrogen
Complex......................................................................................................….37


vi

5.1.5 Geometry Optimization Calculation of two Water-Carbon dioxide
complex……………………………………………………….......……....…...41
5.2 Molecular Orbital Interaction from Gaussian................................................…........44
5.3 Comparison of IR absorption for nitrogen and Water-nitrogen complex……..........45
5.4 Summery of the Results..................................................................................….......47
6. Conclusion and Future work…......................................................................................48
Reference...............................................................................................................…........50
Appendix A……………………………………………………………………………....56
Appendix B……………………………………………………………………….….…..98
















vii

LIST OF TABLES
Table Page
2.1 Fundamental Interaction.................................................................................................5
2.2 Theoretical Methods in Computational Chemistry................................................…....8
5.1 Details of Structure I of H2O-N2.................................................................................23
5.2 Details of Structure II of H
2
O-N
2
.................................................................................23
5.3 5.3 Details of Structure III of H
2
O-N
2
.........................................................................24
5.4 Details of Structure IV of H
2
O-N
2……………………………………………………………………………..
25
5.5 Details of Structure V of H
2
O-N
2
...............................................................................25
5.6 Details of Structure VI of H
2
O-N
2
...............................................................................26
5.7 Calculated Energy of Water-Nitrogen complexes by different methods….................26
5.8 Calculated Energy of Water-Nitrogen complexes at different N-H
Distance........................................................................................................................27
5.9 Details of Structure I of H
2
O-CO
2
…...........................................................................29
5.10 Details of Structure II of H
2
O-CO
2
............................................................................30
5.11 Details of Structure III of H
2
O-CO
2
...........................................................................31
5.12 Details of Structure IV of H
2
O-CO
2
…......................................................................31
5.13 Details of Structure V of H
2
O-CO2………...............................................................32
5.14 Calculated Energy of Water-Carbon dioxide complexes by different
Methods......................................................................................................................32
5.15 Calculated Energy of Water-Carbon dioxide complex at different C-O
Distance.......................................................................................................................33
5.16 Details of Structure I of H
2
O-N
2
…............................................................................38
5.17 Details of Structure II of H
2
O-N
2
…...........................................................................38

viii

5.18 Details of Structure III of H
2
O-N
2
….....................................................................…39
5.19 Details of Structure IV of H
2
O-N
2
……….................................................................40
5.20Calculated Energy of two Water-Nitrogen complexes by different methods…….…40
5.21 Details of Structure I of 2H
2
O-CO
2
….......................................................................41
5.22 Details of Structure II of 2H
2
O-CO
2
………..............................................................42
5.23 Details of Structure III of 2H
2
O-CO
2
……................................................................43
5.24 Calculated Energy of two Water-Nitrogen complexes by different methods............43
5.25 Summery of the Results….........................................................................................47










ix

LIST OF FIGURES
Figure Page
2.1 Summaries of the Non-covalent Interactions……………………………..……...……5
3.1 CO
2
-H
2
O Complex Peaks….........................................................................................18
3.2 N
2
-H
2
O Complex peaks…............................................................................................19
5.1 Structure I of H2O-N
2
…………………………………………………………..……22

5.2 Structure II of H
2
O-N
2
….............................................................................................23

5.3 Structure III of H2O-N
2
…...........................................................................................24

5.4 Structure IV of H2O-N
2
……………………………………………….…..........……24

5.5 Structure V of H2O-N
2
……………………………………………………....………25

5.6 Structure VI of H2O-N
2
……………………………………………………...………26

5.7 Energy vs. Distance diagram of Water Nitrogen complex...........................................28
5.8 Optimized structure of H2O-N
2
……………………………………………...........…28

5.9 Structure I of H
2
O-CO
2
…………………………………………………….……...…29

5.10 Structure II of H
2
O-CO
2
…........................................................................................30

5.11 Structure III of H
2
O-CO
2
…………………………………………………….......…30

5.12 Structure IV of H
2
O-CO
2
……………………………………………………...……31

5.13 Structure V of H
2
O-CO
2
………………………………………….…………...........32


x

5.14 Energy vs. Distance diagram of Water Carbon dioxide complex………………..…34
5.15 Optimized structure of Water Carbon dioxide complex……………………….........34
5.16 Spectra of one Water Nitrogen generated by Gaussian..............................................35
5.17 Spectra of Water Nitrogen obtained from MIS……………………….……….........36
5.18 Spectra of one Water Carbon dioxide generated by Gaussian ...........................…...36
5.19 Spectra of Water Carbon dioxide obtained from MIS………………………......….37
5.20 Structure I of two water-nitrogen complex…………………………………....……37
5.21 Structure II of two water-nitrogen complex…………………………………...……38
5.22 Structure III of two water-nitrogen complex..............................................................39
5.23 Structure IV of two water-nitrogen complex……………………………….....…….39
5.24 Optimized Structure of two water-nitrogen complex..................…...........................40
5.25 Structure I of two water-carbon dioxide complex................................…..................41
5.26 Structure I of two water-carbon dioxide complex………………..........................…42
5.27 Structure I of two water-carbon dioxide complex......................................................42
5.28 Structure I of two water-carbon dioxide complex..........................…........................43
5.29 Molecular orbital interaction between water -nitrogen complex…............................44
5.30 Molecular orbital interaction between water- carbon dioxide
complex……….................................................................................................……44

xi

5.31 Spectra of Nitrogen molecule generated by Gaussian…............................................45
5.32 Spectra of two Water-Nitrogen complexes generated by
Gaussian....................................................................................................................46
5.33 Spectra of Carbon dioxide molecule generated by Gaussian….................................46
5.33 Spectra of Water-Carbon dioxide complex generated by
Gaussian…................................................................................................................47



Reza 1



Chapter 1
Introduction
1.1 Atmospheric Complexes
It is well-documented that the water molecule can form weak (van der Waals)
complexes with atmospheric gases, such as O
2

1, 2, 3
. Much weaker (less than 1kcal/mol)
van der Waals interactions with N
2
can lead to complexes between abundant
atmospheric gases and water. These weak forces include dispersion forces, electrostatic
interactions, and hydrogen bonding. Weak intermolecular interactions are responsible
for solvation and complexation. They affect optical properties and reaction dynamics of
molecular systems
4
.
Global warming and climate change are topics of concern everywhere. The factors
affecting atmospheric changes are diverse and for some changes there is not enough
scientific understanding to grasp their impact. Water vapor plays an important role in the
radiative balance of the earth. Water molecules can absorb both the short-wavelength
solar radiation arriving in the atmosphere and the outgoing infrared (IR) surface
radiation. Water complexes could play a role in the chemical and radiative balance of the
atmosphere if their spectroscopic and photochemical properties are sufficiently different
from those of their monomeric constituent
4
.
Carbon dioxide is well known for its IR energy absorption capacity, or greenhouse
effect. When it forms a hydrated complex, its IR absorption ability may increase. This
argument can be justified if computational simulation is performed on this hydrated
complex.
At Lamar University research had been going on this topic for past several years.
Reza 2



Using matrix isolation spectroscopic experiments, a wealth of infrared spectral data on
atmospheric reactions with water vapor has been obtained that needs a review and
proper interpretation. The spectroscopic information of these complexes is essential to
estimate their atmospheric abundance and quantify their effect on the atmosphere
5
.
Computational chemistry has arisen as a powerful tool to calculate physical and
chemical properties of molecules. The types of predictions possible for molecules and
reactions include heats of formation, bond and reaction energies, molecular energies
and structures, vibration frequencies (IR and Raman spectra), etc.
6
.
Advances in the computational chemistry branch allow the study of the
interaction between two or more molecules
7
. Among developed different methods, the
ab initio methods are the most accurate. Ab initio schemes utilize the supermolecular
approach to study intermolecular interaction energy.
1.2 Overview of the study
We have put emphasis on the computational chemistry simulations to compare
the experimental data obtained from the Matrix Isolation FTIR spectroscopic
investigation. A Hartee-Fock as well as post-Hartree-Fock ab initio computation on
hydrated complex with nitrogen and carbon dioxide using the Gaussian 03 program has
been performed. At first single point energy of this complexes are determined which
help to predict the stability and reaction mechanism. Then the equilibrium geometries
and vibrational frequencies were calculated with the Mөller Plesset perturbation theory
of second order (MP2) as well as Density Functional Theory (DFT). A triple basis set
combined with diffuse functions and polarization functions (6-311++G(2d,2p)) were
used to calculate at the above level of theory. Not only monomer water molecule, but
Reza 3



also multiple water molecules interacted with the same counter species have been
considered. Geometry optimization can tell us the most possible geometry in which
these complexes can be in atmosphere while the frequency shifts were compared and
confirmed with experimental spectra obtains with IR spectroscopy.
The goal of this study is to:
1. Theoretically prove the existence of H
2
O-N
2
and H
2
O-CO
2
Complexes.
2. Determine the single point energy of these water complexes.
3. To find out the optimized structures of H
2
O-N
2,
H
2
O-CO
2,
H2O-N
2
-H
2
O, and
H
2
O-CO
2
-H
2
O

Complexes.
4. Compare the result obtained from the theoretical analysis to the experimental
study.
A brief description of the Matrix Isolation spectroscopy is given in Chapter 3.
Methodology of this study is discussed in Chapter 4. Chapter 5 contains the results and
discussion. Conclusion and scopes of future study is discussed in chapter 6.









Reza 4



Chapter 2
Literature Review

2.1. Fundamental Interactions
In nature four types of interactions are found. They are strong, weak, electromagnetic
and gravitational
8
. In table 2.1 a summary of these interactions is shown.
Electromagnetic interaction is an interaction between charged particles arising from
their electric and magnetic fields. They are long range attractions or repulsions between
charged particles. These forces are responsible for the formation of covalent and
noncovalent bonds.
In noncovalent bonds these interactions may be intermolecular or intramolecular.
Interactions between two or more molecules are called intermolecular interaction while
interaction between the atoms within a molecule are called intramolecular interaction
9
.
In Figure 2.1 different types of noncovalent interactions are shown. Our focus is only on
noncovalent intermolecular interactions, which are very important for this study.
2.1.1. Noncovalent Intermolecular Interactions
Intermolecular interactions occur between all types of molecules or ions in all state of
matter. Their range varies from the strong, long distant electromagnetic force to
relatively weak dispersion forces.
These intermolecular interactions can be divided into four broad categories which are
electrostatic, repulsion-exchange, polarization and dispersion interaction.

Reza 5



Table 2.1 Fundamental Interaction
10



Figure 2.1 Summaries of the Non-covalent Interactions
10
Reza 6



Therefore, the total intermolecular interaction energy for a system is defined as
the sum of these four intermolecular energies:
E
int
= E
es
+ E
pol
+ E
dis
+ E
ex
(1)

Where, E
es
, E
pol
, E
dis
, E
ex
, are electrostatic, polarization, dispersion and exchange
respectively.
-Repulsion – exchange interactions are for the overlapping of charge of occupied orbitals.
It also originated from the exchange effect.
-Electrostatic interactions are between two molecules with permanent dipole. Some
types of electrostatic interaction are charge – charge, charge – dipole, dipole – dipole.
-Polarization interactions occur between two molecules when one has a permanent dipole
and the other has an induced dipole. Sometimes it occurs in non-polar molecule also for
the movement of the valence electron which causes instantaneous dipoles.
-Dispersion interactions occur between two molecules when one has induced dipole
and the other has an instantaneous dipole. It is generally observed in non-polar
molecules and is not considered simple electrical attractions. These types of interactions
are very weak until the molecules or ions are very close to each other
11
.
2.2. Computational Chemistry
Computational chemistry is defined as the application of chemical, mathematical
and computational skills to the solutions of chemical problems
6, 12
. Different types of
theoretical methods have been developed to approach computational chemistry. The
grade of rigor of calculations is the differentiating point among these methods. The most
acceptable methods are: Molecular Mechanics, Semi-empirical, and ab Initio. General
Reza 7



characteristics for each method are summarized in table 2.2.
2.2.1. Ab Initio Methods
Ab initio translated from Latin means “from first principles.” This refers to the fact
that no experimental data is used and computations are based on quantum mechanics. Ab
initio method uses Schrödinger’s equation as the start point for the calculations.
In ab initio methods solutions of the Schrödinger equation is done using a series
of rigorous mathematical approximations. Ab initio calculations are defined by “model
chemistry”. This model includes the choice of Methods and Basis set. The ab initio
method is classified in two subclasses: Hartrees Fock and Post Hartree Fock methods.














Reza 8



Table 2.2 Theoretical Methods in Computational Chemistry
10

2.2.1.1 Hartree-Fock Method (HF)
Hartree-Fock theory is the most common type of ab initio calculation. It provides a
reasonable model for a wide range of problems and molecular systems. However it has
some limitations. They arise from the fact that Hartee-Fock theory does not include a full
treatment of the effects of electron correlation: the energy contributions arising from
electron interacting with one another. For systems and situations where such effects are
important, Hartee-Fock results may not be satisfactory
6
. Hartree-Fock theory often
Reza 9



provides a good starting point for more elaborate theoretical methods which are
better approximations to the electronic Schrödinger equation.
2.2.1.2 Post Hartree-Fock Methods
The electron correlation effects are considered in Post Hartee-Fock methods. Where in
Hartee-Fock method these effects are approximated by the interaction of each electron
with an average electric field produced by all the remaining electrons in the system,
the post Hartee-Fock methods consider the full extent of many particle effects. Although
the correlation energy which originated from the electron correlation is a small percentage
of the total energy of the system but cannot be neglected. So a number of different
techniques have been developed to determine the correlation energy. These techniques are
known as electron correlation met hods or post -Hartree-Fock met hods. The most
widely used are the Configuration Interaction(CI), perturbation techniques such
asMoller-Plesset perturbation (MP* ,*=2,3,4...) and cluster expansion such as Coupled
Clusters (CC)
10
.
2.2.1.3 Basis Set
A basis set is the mathematical description of the orbitals within a system (which in
turn combine to approximate the total electronic wave function) used to perform the
theoretical calculation. Larger basis sets more accurately approximate the orbitals by
imposing fewer restrictions on the locations of the electrons in space
6
.
There are two types of basis functions, commonly used in electronic structure
calculation: Gaussian type orbitals (GTO) and slater type orbital (STO).


Reza 10



Classification of Basis Sets
The classification of basis sets can be done according to the number of basis
functions used to describe each atomic orbital in: minimal, splitting the minimal and
extended basis set.
Minimal Basis Set
Contain the minimum number of basis functions needed to describe each atom. For
example, for hydrogen and helium, this means a single s-function. For the first row in
the periodic table, i t means two s-functions (1s and 2s) and one set of p-functions (2p
x
,
2p
y
, 2pz).
Splitting the minimal basis set
Split orbitals: The next improvement in the basis set is including two or three
basis functions for each atomic orbital. For example double zeta (DZ) and triple zeta
(TZ) basis set. A DZ basis set employs two s-functions for hydrogen (1s and 1s’),
four s- functions (1s, 1s’, 2s and 2s’) and two p-functions (2p and 2p’) for first row
in the periodic table.
Split valence: The orbitals corresponding to the inner shell of electrons are
described with only one basis function while the orbitals corresponding to the valence
shell electron are described with two or more basis functions.
Extended basis set
The "extended" basis sets consider the higher orbitals of the molecule and account for
size and shape of molecular charge distributions. The improvement consist in
including higher angular momentum basis function to account for distortions, such as
polarization and diffusion, caused by the interactions of neighboring atoms.
Reza 11
















When two atoms are close enough the distortion of electron density happen due to the
influence of the other nucleus. This charge charge redistribution causes a polarization
effect. For example, it can distort the spherical 1s orbital on hydrogen by mixing in
with an orbital with p symmetry. The positive lobe at one side increases the value of
the orbital while the negative lobe at the other side decreases the orbital. Thus it
becomes polarized
10
.


Similarly it can polarize the p orbitals if it is mix in with an orbital of d symmetry.



These additional basis functions are called polarization functions.
In some cases like in an excited state the normal basis functions we use are not
adequate. To model this kind of state some additional basis functions called diffuse
functions are used.
Pople Style Basis Set
There are many different basis set available in the literature or built into
programs. Among the most used representative notations of Pople style basis set are:
STO-nG basis set, slater type orbital consisting of n primitives Gaussian type
orbital (PGTO). This basis set is a widely used as minimum basis set.
k-nlmG basis set. This basis set is of the split valence type. In this notation k is
the numbers of PGTOs functions that represent the inner shell electrons or core
Reza 12



orbital, while nlm indicates both how many the valence orbitals are split, and how
many PGTOs function are used for their representation.
Two values (nl) indicate a split valence, while three values (nlm) indicate a triple
split valence. The values before the G indicate the s and p – functions in the basis set.
To each one of these basis sets, diffuse and/or polarization functions can be added.
Diffuse functions are s and p – functions, denoted by + for heavy atoms and ++ for
hydrogens and consequently go before the G. Polarization functions are indicated for a
letter inside parenthesis or an asterisk after the G, with a separate designation for
heavy atoms and hydrogens. For example, the 6-31+G (d) or 6-31+G* basis set is a
split valence basis set with one set of diffuse sp-functions on heavy atoms only
and a single d-type polarization function on heavy atoms
6,10,11
.
2.2.2. Density Funtional Theory –DFT
The DFT methods are considered an ab initio method, but different from other ab
initio methods because the wavefunction is not used to describe a molecule, instead the
electron density is used
6
. For this reason some theoreticians disagree with this. DFT
includes the effect of electron correlation. In DFT theory electron correlation is
computed as a functional of the electron density, ρ. The functional employed is
computed separately into several components according to the Kohn-Sham equation:
E = E
T
+ E
V
+ E
J
+ E
XC
(2)
Where, E
T
is the kinetic energy term that contain the motions of electrons, E
V
is
the potential energy term that includes nuclear-nuclear and nuclear-electron
interactions, E
J
is the electron-electron repulsion term and E
XC
is the exchange-
correlation term that includes the electron correlation.
Reza 13



Two types of functionals are used here. These are traditional and hybrid functionals.
The local and gradient-corrected or non-local functionals are the traditional functionals.
The most popular gradient-corrected exchange functional is one proposed by Becke
12
(B)
and the most usually used gradient-corrected correlation functional is the Lee, Yang and
Parr
13
(LYP).
The hybrid functionals define the exchange functional as a linear combination of
Hartree-Fock, local and non-local exchange terms; and the correlation functional as a
local and/or non-local correlation terms. The most known is the Becke’s three-
parameter formulation, B3LYP.
2.2.3. Types of Calculations
The ab initio methods can be used to calculate structural and thermodynamic
properties such as
6
:
1. Molecular Geometry
2. Vibrational Frequencies-Force Constants - Vibrational Spectrum
3. Intermolecular Interaction energies
4. Solvation properties
5. Energy Potential Surfaces
6. Energy Barriers to Reactions - Internal, Rotational or Inversion
7. Chemical Reactions - Transition State Theory
8. Ionization Potentials
2.2.4. Terminology
Terminology used in this work is the standard nomenclature of the reference
6

energy_method/energy_basis_set//geometry_method/geometry_basis_set
Reza 14



Where the model to the left of the double slash is the one at which the energy is
computed, and the model to the right of the double slash is the one at which the
molecular geometry was optimized.
2.2.5. Intermolecular Interaction Energy Calculation
The ab initio methods are the most accurate for calculating intermolecular
interaction energy. Ab initio schemes utilize the perturbation and supermolecular
methods as approaches to study the intermolecular interaction energy.
The perturbation methods

treat the interaction between the subsystem wave
functions as a perturbation and the interaction energy is evaluated by perturbation
theory
14
. The different interactions energies, electrostatic energy, polarization energy,
dispersion energy and exchange energy, are calculated separately. Therefore the total
energy is a summation of these contributions.
The supermolecular methods have been the most common procedure for the
calculation of interaction energies
10
.
2.2.5.1 Supermolecular Approach
If we consider a chemical system AB composed of two interacting fragments A and
B. The interaction can be defined as
15, 16
:
E
int
= E
complex
– ∑ E
molecule
(3)

Where, E
int
is the intermolecular interaction energy or binding energy, E
complex
the
energy of the complex AB and ∑ E
molecule
is the total energy of isolated molecules A
and B.



Reza 15



2.2.5.2. Effective ab initio methods for supermolecular approach
Many ab initio methods such as HF, MP2, and DFT can be used for
intermolecular interaction energy calculation, using the supermolecular approach.
However, not all of them will give satisfactory result.
The Hartree-Fock method does not consider the dispersion energy, which is
involves in electron correlation between electrons on different molecules.
In the post-Hartree–Fock methods, the electron correlation is evaluated.
Therefore, the interaction energy calculated with these methods should give more
value. The post Hartree Fock methods with less computational cost is second–order
Møller - Plesset theory (MP2), this methods give accurate intermolecular interaction
energies
17
.
DFT method demand much less computationally cost than ot her post-Hartree-
Fock methods. The disadvantage of the DFFT method is it cannot evaluate the
dispersion energy. This happens because DFT method does not have a correlation
functional that can describe the dispersion energy
18, 19
.
2.2.7 The Water Complexes
Molecular complexes in the Earth’s atmosphere are of two types: collisional, such as
the oxygen dimer O2·O2, or bound– van der Waals complexes – like the water vapor
dimer H2O-H2O. In both cases, it can be assumed that they are at equilibrium with their
parent molecules in the atmosphere. Their formation and loss processes can then be
expressed as a reaction of the type [A] + [B]=[A−B], with an equilibrium constant
usually noted Kp. These complexes have a short atmospheric lifetime (few picoseconds)
and a broad spectrum for absorption of solar radiation. They can be observed in the
Reza 16



UV/Visible spectral ranges. These measurements are often used to obtain cloud top
heights. The abundance of collision complexes depends on the partial pressure of the
parent molecules, such as O
2
, H
2
O or N
2
, and on the temperature. Their atmospheric
abundance and variations are well documented. On the other hand, there have been no
reports of explicit detection of bound complexes in the atmosphere so far. In the past 2–3
decades, lots of laboratory and theoretical studies of bound complexes have been
published.
20-25

However in most recent studies it has been found that the inferred abundance of water
complex at the Earth’s surface is at the sub-ppmv level. This is comparable to the surface
concentrations of CO or N
2
O and shows that knowledge of the abundance of water
vapour complexes is undeniably important to further our understanding of tropospheric
processes.
26










Reza 17



Chapter 3
Previous Work

3.1 Overview of the Study
Matrix isolation spectroscopy was developed by George Pimentel in solidified noble
gases, which act as trapping media for reactive species
27
.However the experimental
advances were very small as temperature reached was about 66K which is not enough to
hold neon, argon or other noble gases used for trapping
28
. Now a day’s equipment like
FTIR has made matrix isolation spectroscopy more simple and interesting.
The experimental study was based on Matrix Isolation (MI) coupled with Fourier
Transform Infrared Spectroscopy. In this technique, the species to be observed are
trapped in a non-reactive substance like argon, nitrogen, etc. at very low temperature. The
species is referred to as the guest and the non-reactive substance is referred to as the host.
The guest and host molecules are deposited on a cold window present inside the matrix
isolation chamber. The choice of the host and cold window material is mainly dependent
on the kind of experiments to be carried out and also the cost factor.
This method allows a direct search for the weak hydrated complexes. These
complexes have a very short lifetime under normal temperature and pressure. MI is a
good method to increase the life time of these complexes and study them. Gas phase
interaction of the reactive species was avoided by depositing the sample gases using
separate deposition ports and mixing cylinders. MI is sensitive technique and even a
slight change in the vacuum or the temperature during experimentation can change the
outcome of the experiment.
Reza 18



3.2 Carbon dioxide Experiment
Carbon dioxide used in this experiment was of research grade manufactured by Air
Liquid. The experiment was carried out at a temperature of 10-11K and at a pressure of
5.5 E-5 Pa. CO
2
was deposited at the rate of 0.54 cc/min for five minutes. The experiment
was carried out for a period of about 7 hours. This is a three layer deposition experiment
in which the CO
2
was deposited for 5 minutes on the cold window and the spectra
recorded for an hour and likewise a third deposition was done and the spectra recorded.
Analysis of the spectra showed that water-carbon dioxide complexes were formed
during the course of the experiment an seen to increase. The peak at 1599 cm
-1
, 3635 cm
-1

and 3727 cm
-1
were assigned to water-carbon dioxide complex. The basis for this
assignment is from available literature.

Figure 3.1 CO
2
-H
2
O Complex Peaks
29

3.3 Nitrogen Experiment
1500 cc of pure nitrogen was stored in the mixing cylinder to deposit on the cold
window. Nitrogen was deposited on the cold window for 20 minutes with a flow rate of
Reza 19



0.5 cc/min. After deposition spectra were recorded every 10 minutes for 2 hours. After
two hours, nitrogen was again deposited for another 20 minutes maintaining the same
flow rate and again spectra were recorded as mentioned above. The above procedure was
done again for a third time and thus nitrogen was deposited layer by layer. Figure 3.2
shows the spectra recorded at 0. 110. 142, 252 and 397 minutes of the experiment.

Figure 3.2 N
2
-H
2
O Complex peaks
30








Reza 20



Chapter 4
Methodology
4.1 Instruments


Dell workstation with dual processors and 4 Gb RAM was used to perform the
theoretical calculations. All calculations were performed with the Gaussian 03 systems
of programs
31
. The structures of all molecules were modeled and visualized using
Gauss view program
32
.

4.2 Computational Methods
This section is divided into two parts. In the first part we performed the
geometry optimization, and vibrational frequencies with their infrared
intensities calculations for the water complexes. In the second part, we compared the
result from the Gaussian with the experimental data we already have. DFT, MP2 and
MP4 methods were evaluated and compared to determine the magnitude of difference
in theoretical treatments.
4.2.1 Geometry Optimization and Vibrational Frequency calculations
In this study, we have considered several model of water-nitrogen and water–
carbon dioxide complex. These models were visualized using the Gauss View
programs
33
.
4.3 Computational Details
Full geometry optimization calculations using Gaussian 03 packages of
programs
34

were made for two lower-energy conformations of Water complexes. The
optimization was performed using MP2, MP4 and DFT methods
35-39
. Basis set effects
Reza 21



were evaluated for the two methods using the family of basis set from the 6-31G up to
the 6-311+ (d, p).
In the DFT calculations we used the hybrid density functional B3LYP

11, 12.
In this
hybrid functional, the exchange functional -B3- correspond to Becke-3–Parameter and
the correlation functional –LYP- correspond to Lee-Yang-Parr.
We compare B3LYP and MP2 predictions of internal coordinates (bonds, angles
and dihedral angles) against structural parameters obtained from the X-ray diffractions
of water complexes. The geometry of the two conformers was optimized to better than
0.0001 Å for bond distances and 0.1° for bond angles. The convergence was, for all
conformations and basis sets, of at least 10
-9
on the density matrix, and the RMS force
less than 10
-4
a. u. for the optimized structures.
Vibrational frequencies calculations were performed for the two lower-energy
conformers optimized of the water complexes using B3LYP method with
different basis sets. Normal–mode analysis was carried out for the optimized
geometries and Infrared (IR) spectra were obtained. We compare the theoretical
frequencies and spectra predicted using B3LYP/6-311+G (d, p) for the two conformers
against experimental frequencies and spectra of water complexes. The spectra were
simulated with a resolution arbitrary of 5 cm
-1
. The vibrational motions corresponding
to each normal mode were determined using Gauss View interactive visualization and
animation program
30
.




Reza 22



Chapter 5
Results and Discussion

5.1 Geometry Optimization and Vibrational Frequency Calculations for Water
Complexes
5.1.1. Geometry Optimization Calculation of one Water Nitrogen Complex
Non-local DFT

and MP2 calculation performed in this work yielded lower- energy
conformation of water-nitrogen complex
31-36
. Six geometric configurations for the
complexes have been considered at first. They are depicted in to figure 5. 1-5.6.
and details of these figures are described in table 5.1-5.6. In the table NA, NB, NC refer
Z-matrix coordinates where X, Y, Z refer the Cartesian coordinates. Dihedral refers the
angle between the planes. The atoms were numbered to specify the optimized
structural parameters, i.e. bond lengths and bond angles. The geometry of two
conformers was optimized to better than 0.001 Å for bond distances and 0.1° for bond
angles. The convergence was, for all conformations and basis sets, of at least 10
-9
on
the density matrix, and the RMS force less than 10
-4
a. u. for the optimized structure.


Figure 5.1 Structure I of H
2
O-N
2
Reza 23



Table 5.1 Details of Structure I of H
2
O-N
2





Figure 5.2 Structure II of H
2
O-N
2

Table 5.2 Details of Structure II of H
2
O-N
2



Reza 24





Figure 5.3 Structure III of H2O-N
2

Table 5.3 Details of Structure III of H
2
O-N
2





Figure 5.4 Structure IV of H2O-N
2
Reza 25



Table 5.4 Details of Structure IV of H
2
O-N
2


Figure 5.5 Structure V of H2O-N
2
Table 5.5 Details of Structure V of H
2
O-N
2


Reza 26




Figure 5.6 Structure VI of H2O-N
2
Table 5.6 Details of Structure VI of H
2
O-N
2


Table 5.7 shows the energy calculated by various methods for the above depicted
geometric configuration.
Table 5.7 Calculated Energy of Water-Nitrogen complexes by different methods

Method

RHF MP2 MP4 DFT
Basis set 3-21 G 6-311++G 6-311++G 6-311++G
Structure 2D,2P 2D,2P B3LYP
I -183.869272952 -185.005269629 -185.005269629 -186.004558257
II -183.886002560 -185.029869878 -185.029869878 -186.025318281
III -183.884221702 -185.030112860 -185.030112860 -186.024301519
IV -183.887716898 -184.986862636 -184.986862636 -185.974836132
V -183.887518356 -185.030575601 -185.030575601 -186.025601206
VI -183.868337987 -185.011426403 -185.011426403 -186.008296680
Reza 27




From the table it is clear that Structure V gives the minimum energy in each method
except the Restricted Hartee Fock (RHF).
So further analysis has been done with the Structure V. Minimum energy at different
N-H distance have been calculated for Structure V and shown in Table 5.8 and energy
vs. distance graph is plotted in Figure 5.7.
Table 5.8 Calculated Energy of Water-Nitrogen complexe at different N-H Distance

H2O-N2
Energy
N-H distance MP2
1.47663 -184.958069
1.6138 -184.9701124
1.73684 -184.976853
1.8138 -184.9797468
1.90332 -184.9821955
2.01176 -184.9842027
2.11176 -184.9854072
2.2113 -184.9861899
2.31176 -184.986693
2.4138 -184.9870032
2.5138 -184.9871745
2.6138 -184.9872583
2.7138 -184.9872858
2.8138 -184.9872776
2.9138 -184.9872484
3.01318 -184.9872078
3.11318 -184.9871616
3.21318 -184.9871139
3.42365 -184.9870184
3.53612 -184.9869728
3.72656 -184.9869058
3.91795 -184.9868507
4.72189 -184.9867096

Reza 28





Figure 5.7 Energy vs. Distance diagram of Water Nitrogen complex

From the above diagram it is confirmed that the energy drops up to a certain distance
and it became constant. It is also well established from previous study
50,51
. We found the
minimum energy at a distance of 2.6138. Optimized structure is been shown in Figure
5.8.

Figure 5.8 Optimized structure of H
2
O-N
2

-184.99
-184.99
-184.98
-184.98
-184.97
-184.97
-184.96
-184.96
-184.95
1 1.5 2 2.5 3 3.5 4 4.5 5
E
n
e
r
g
y

i
n

H
a
r
t
e
e

N-H distance in Angstroms
N-H:2.618 A
o
,
<NHO: 173.4
o
,
N=N: 1.113 A
o
,
NNH: 177.30
o
,
HOH:104.59A
o
Reza 29



5.1.2 Geometry Optimization Calculation of one Water Carbon dioxide Complex

Similar calculations have been carried out for water-carbon dioxide complex. Figure
5.9- 5.13 presents the different geometric configuration of water-carbon dioxide
complex which has been considered for geometric optimization. The optimization was
performed using MP2 method.




















Figure 5.9 Structure I of H
2
O-CO
2
Table 5.9 Details of Structure I of H
2
O-CO
2



Reza 30





Figure 5.10 Structure II of H
2
O-CO
2
Table 5.10 Details of Structure II of H
2
O-CO
2





Figure 5.11 Structure III of H
2
O-CO
2
Reza 31



Table 5.11 Details of Structure III of H
2
O-CO
2



Figure 5.12 Structure IV of H
2
O-CO
2
Table 5.12 Details of Structure IV of H
2
O-CO
2



Reza 32




Figure 5.13 Structure V of H
2
O-CO
2

Table 5.13 Details of Structure V of H
2
O-CO
2


Table 5.14 shows the energy calculated by various methods for the above depicted
geometric configuration.

Table 5.14 Calculated Energy of Water-Carbon dioxide complexes by different
methods


Method

RHF MP2 MP4 DFT
Basis Set 3-21 G 6-31++G 6-31++G 6-311++G
Structure 2D,2P 2D,2P B3LYP
I
-
262.141516566
-
263.721476918
-
263.721476736
-
265.097528950
II
-
262.098714965
-
263.622527714
-
263.622527714
-
265.071747667
III
-
262.135220577
-
263.490383238
-
263.490383238
-
265.100496044
IV
-
262.127789033
-
263.658439438
-
263.658439438
-
265.097755308
V
-
262.112889952
-
263.636419993
-
263.636419993
-
265.082765115
Reza 33




From the table it is clear that Structure I gives the minimum energy in each method
except the DFT method.
So further analysis has been done with the Structure I. Minimum energy at different
C-O distance have been calculated for Structure I and shown in Table 5.15 and energy
vs. distance graph is plotted in Figure 5.14
Table 5.15 Calculated Energy of Water-Carbon dioxide complex at different C-O
Distance
Energy
C-O Length DFT
5 -265.1006114
2.94 -265.1029411
2.64017 -265.1022879
2.54017 -265.1014094
2.44017 -265.0999122
2.34017 -265.09752895
2.24017 -265.09389581
2.14017 -265.08852994
2.04017 -265.08082351
1.94017 -265.07004507
1.84017 -265.05536322
1.74017 -265.03583987
1.64017 -265.01050303
1.54017 -264.97825510
1.44017 -264.937507


Reza 34




Figure 5.14 Energy vs. Distance diagram of Water Carbon dioxide complex
From the above diagram it is confirmed that the energy drops up to a certain distance
and it became constant. It is also well established from previous study
50,51
. We found the
minimum energy at a distance of 2.6138. Optimized structure is been shown in Figure
5.15.

Figure 5.15 Optimized structure of Water Carbon dioxide complex
-265.12
-265.1
-265.08
-265.06
-265.04
-265.02
-265
-264.98
-264.96
-264.94
-264.92
1 1.5 2 2.5 3 3.5 4 4.5 5 5.5
E
n
e
r
g
y

i
n

H
a
r
t
e
e

C-O distance in Angstroms
C-O: 2.94 A
o
,
<OCO: 86.65
o
C=O: 1.160 A
o
Reza 35



5.1.3 Vibrational Frequencies Calculation

Vibrational frequencies for the two complexes were determined through normal -
mode anal ysis. In this analysis, the two complexes exhibited real frequencies.
Vibrational frequencies were calculated using B3LYP method with the family of
basis sets 6-31G to 6-311+G(d,p), for the complexes.
The values that more resembled the experimental data were the calculated with the
6-31G (d) and 6-311+G (d, p) basis set. Figure 5.16, 5.17 shows a comparison of the
calculated infrared spectra performed with B3LYP method using the 6-31G(d) and
basis set and the spectra obtained from the experiment, for the water nitrogen complex.




Figure 5.16 Spectra of one Water Nitrogen complex generated by Gaussian












Reza 36






Figure 5.17 Spectra of Water Nitrogen complex obtained from Matrix Isolation
Spectroscopy (MIS)
The peak values obtained from Gaussian are at 737.805 cm
-1
, 1658.54 cm
-1
, 2006.1
cm
-1
and 4000 cm-1which are comparable to the peak value obtained from experimental
data 797 cm
-1
,

1684 cm
-1
and 2348 cm
-1
.
Similar charts have been plotted for water carbon dioxide complex and showed in
Figure 5.18 and 5.19


Figure 5.18 Spectra of one Water Carbon dioxide generated by Gaussian
2140
1684
797
Reza 37





Figure 5.19 Spectra of Water Carbon dioxide obtained from MIS
The peak values obtained from Gaussian are at 1647.81 cm
-1
and 3864.9 cm
-1
which
are comparable to the experimental data 1687 cm
-1
and 3615 cm
-1
.
5.1.4 Geometry Optimization Calculation of two Water Nitrogen Complex
Although our study has confirmed the molecular structure of Water nitrogen and
water carbon dioxide complex, complex with multiple water is also a concern. Four
Geometric configurations with two water molecule and one nitrogen molecule has been
studied and depicted in Figure 5.20- 5.23. Details of this figures are described in tabular
form from table 5.16-5.19 Minimum energy of each configuration is also calculated and
showed in table 5.19

Figure 5.20 Structure I of two water-nitrogen complex
1687
3615
Reza 38




Table 5.16 Details of Structure I of H
2
O-N
2





Figure 5.21 Structure II of two water-nitrogen complex

Table 5.17 Details of Structure II of H
2
O-N
2


Reza 39





Figure 5.22 Structure III of two water-nitrogen complex

Table 5.18 Details of Structure III of H
2
O-N
2




Figure 5.23 Structure IV of two water-nitrogen complex

Reza 40



Table 5.19 Details of Structure IV of H
2
O-N
2


Table 5.20 Calculated Energy of two Water-Nitrogen complexes by different
methods

Method

RHF MP2 MP4 DFT
basis set 3-21 G 6-31++G 6-31++G 6-311++G
Structure 2D,2P 2D,2P B3LYP
I
-
259.4360565
-
259.4440043
-
259.4440043
-
259.4340343
II
-
259.4303925
-
260.9596558
-
260.9596558
-
262.4346973
III
-
259.4419479
-
260.9826086
-
260.9826086
-
262.4546049
IV
-
259.4757560
-
261.0862785
-
261.0862785
-
262.4883963

It is clear that Structure IV is exhibiting the minimum energy. Optimized structure of
structure IV is shown in Figure 5.24.



Figure 5.24 Optimized Structure of two water-nitrogen complex

Reza 41



We have found an E
h
= -262.488399096 for this optimized structure. The point group
is Cs

and <OHN=168.36617
o

5.1.5 Geometry Optimization Calculation of two Water-Carbon dioxide Complex
Water carbon dioxide complex with two water molecule is also been studied. Three
geometric configurations is analyzed, those are depicted from Figure 5.25-5.27. Their
details have been described in tabular form from table 5.20-5.22. Minimum energy of
each configuration is also calculated and showed in table 5.23


Figure 5.25 Structure I of two water-carbon dioxide complex
Table 5.21 Details of Structure I of 2H
2
O-CO
2

Reza 42




Figure 5.26 Structure II of two water-carbon dioxide complex
Table 5.22 Details of Structure II of 2H
2
O-CO
2


Figure 5.27 Structure III of two water-carbon dioxide complex
Reza 43



Table 5.23 Details of Structure III of 2H
2
O-CO
2



Table 5.24 Calculated Energy of two Water-Nitrogen complexes by different
methods


Method

RHF MP2 MP4 DFT
basis set 3-21 G 6-31++G 6-31++G 6-31++G
Structure 2D,2P 2D,2P B3LYP
I
-
337.747553358
-
339.798041829
-
339.798041829
-
341.565330599
II
-
337.691043630
-
339.669707515
-
339.669707515
-
341.539613743
III
-
337.661450215
-
339.618675197
-
339.618675197
-
341.493912698

Structure I exhibiting the minimum energy. Optimized structure is shown in Figure 5.28.

Figure 5.28 Optimized structure of two water-carbon dioxide complex
Reza 44



5.2 Molecular Orbital Interaction from Gaussian
From Gaussview 03 we have also generated molecular interaction diagram for water-
nitrogen complex and water-carbon dioxide complex. These diagrams show the extent of
interaction by similar color.
Molecular orbital interaction diagram of water nitrogen complex and water carbon
dioxide complexes are shown in Figure 5.29 - 5.30

Figure 5.29 Molecular orbital interaction between one water -nitrogen complex

Figure 5.30 Molecular orbital interaction between water –carbon dioxide complex
Reza 45



From careful observation of the above four figures it can be deduced that water-carbon
dioxide complexes have shown a greater orbital interaction in comparison to water-
nitrogen complexes. The single point energy, calculated for these complexes also support
this. We have found much larger single point energy for water-nitrogen complex (E
h
= -
186.0 and -262.48) than water-carbon dioxide complex (E
h
=-265.11 and -341.56).
5.3 Comparison of IR absorption for nitrogen and Water-nitrogen complex:
Spectra of only nitrogen molecule and only carbon dioxide molecule are also
generated. In Figure 5.31 we can see that no IR absorbance is occurring while in Figure
5.32 some IR absorbance is clearly seen. So nitrogen molecule does not absorb IR but
Water-Nitrogen complex does.


Figure 5.31 Spectra of Nitrogen molecule generated by Gaussian
Reza 46




Figure 5.32 Spectra of two Water-Nitrogen complex generated by Gaussian
From the spectra of carbon dioxide molecule (Figure 5.33) and Water-Carbon dioxide
complex (Figure 5.34) it is observed that the complex has a wide range of IR absorbance
than the molecule alone.

Figure 5.33 Spectra of Carbon dioxide molecule generated by Gaussian
Reza 47




Figure 5.33 Spectra of Water-Carbon dioxide complex generated by Gaussian
5.4 Summery of the Results
Table 5.4 shows the summery of all the calculated results
Table 5.25 Summery of the Results

H
2
O-N
2
H
2
O-N
2
-H
2O
H
2
O-CO
2

H
2
O-CO
2
-
H2O
Bond Distance in
angstrom
2.41318 2.45709 2.86451 2.94447
Energy (Eh)
-186.0267798 -262.4883991
-
265.115709 -341.5655444
Symmetry
C
s
C
s

C
1

C
s

IR Frequencies
737.80 cm
-1
,
1658.54 cm
-1

and 2006.1
cm
-1

1671.93 cm
-1
and 3839.61
cm
-1

1647.81
cm
-1
and
3864.9 cm
-1

1630.29 cm
-1
and 2402.28
cm
-1




Reza 48



Chapter 6
Conclusion and Future Works
Regarding water-nitrogen complex, the vibrational frequencies generated from
Gaussian are at 737.805 cm
-1
, 1658.54 cm
-1
, 2006.1 cm
-1
and 4000 cm
-1
which are within
the error tolerance limit of experimentally obtained wavenumbers of 797 cm
-1
,

1684 cm
-1
and 2348 cm
-1
.

For one water-nitrogen complex we obtained a geometry which has a
point group of C
s
, E
h
=-186.03. For two water-nitrogen complex we got a point group of
C
s
, E
h
= -262.48 and vibrational peak at 1671.93 cm
-1
and 3839.61 cm
-1
.
Similar satisfactory wavenumbers have been found for water-carbon dioxide complex.
Peaks at 1687 cm
-1
and 3615 cm
-1
were found from experimental data while peaks at
1647.81 cm
-1
and 3864.9 cm
-1
(for one water-carbon dioxide) and 1630.29 cm
-1
and
2402.28 cm
-1
(for two water-carbon dioxide) have been found from Gaussian program.
From this research, we may conclude that water-carbon dioxide complexes have
higher single point energy than water-nitrogen complexes. The molecular orbital
interaction diagram generated from Gaussian program also indicated this fact.
We also concluded that nitrogen molecules do not show any IR absorbance value, but
water-nitrogen complexes have some IR absorbance. This indicates that if this complex
is present in the atmosphere it may enhance the greenhouse effect. A wider range of IR
absorbance value has been found for water-carbon dioxide complex than for carbon
dioxide alone. This extensive IR absorbance by water-carbon dioxide complex also
indicates that it may play an important role in greenhouse effect. In addition, single point
Reza 49



energy of complexes decreases while increasing the van der Waals distance, and after a
certain distance it becomes constant.
Lastly, larger hydrated complexes with more than three water molecules are expected
to have similar properties which we found in this work. However, analysis of larger
molecules is beyond the scope of this study. So in presence of higher computational
facility, larger complex with higher basis set can be simulated in Gaussian.












Reza 50



References
1. Igor M. Svishchev and Russell J. Boyd, “van der Waals Complexes of Water with
Oxygen and Nitrogen: Infrared Spectra and Atmospheric Implications,” Journal of
Physical Chemistry 102 (1998): 7294-7296.
2. H.G. Kjaergaard, G.R. Low, T.W. Robinson, D.L. Howard, Journal of Physical
Chemistry 106 (2002): 8955.
3. H.M. Lee and K.S. Kim, Molecular Physics 100 (2002): 875.
4. V. Vaidaand and J. E. Headrick, “Physicochemical Properties of Hydrated
Complexes in the Earth's Atmosphere,” Journal of Physical Chemistry 104 (2000): 5401-
5412.
5. H. G. Kjaergaard, T. W. Robinson, D. L. Howard, J. S. Daniel, J. E. Headrick, and
V. Vaida, “Complexes of Importance to the Absorption of Solar Radiation,” Journal of
Physical Chemistry A 107 (2003): 10680-10686.
6. Foresman, J.B. and A. Frisch. Exploring Chemistry with Electronic Structure
Methods. Pittsburgh, PA: Gaussian Inc., 1996.
7. Y. Ma, “Determination of NonCovalent Intermolecular Interaction Energy from
Electron Densities,” (Ph.D. Dissertation, University of New Orleans, New Orleans, 2004)
8. James O’Connell, “Comparison of the Four Fundamental Interactions of Physics,”
The Physics Teacher (1998): 36, 27.
Reza 51



9. S. S. Zumdahl, Chemical Principle (New York: Houghton Mifflin, 2002) Chapter 4.
10. Liliana F. Alzate Rodríguez, “Ab Initio and DFT Calculations of TNT and its
interaction with clay minerals: changes on TNT spectroscopic signature,” (Master’s
thesis, University of Puerto Rico, 2005).
11. I. N. Levine, Physical Chemistry (New York: Mc Graw-Hill, 2006) Chapter 22.
12. F. Jensen, Introduction to Computational Chemistry. England: John Wiley & Sons
Ltd., 1999.
13. A. D. Becke. “Density-Functional. Thermochemistry. III. The Role of Exact
Exchange,” Journal of Chemical Physics 98 (1993) 5648-5652.
14. P. Arrighini, Intermolecular Forces and Their Evaluation by Perturbation Theory.
Berlin: Springer, 1981.
15. F. B. van Duijneveldt and Van Lenthe, “State of the Art in Counterpoise Theory,”
Chemical Reviews 94 (1994): 1873-1885.
16. B. Jeziorski, R. Moszynski and K. Szalewicz, “Perturbation Theory Approach to
Intermolecular Potential Energy Surfaces of van der Waals Complex,” Chemical Reviews
94 (1994): 1886-1930.
17. G. Cholasinski and M. Gutowski, “Weak Interactions between Small Systems.
Models for Studying the Natural of Intermolecular Forces and Challenging Problems
for ab Initio Calculations,” Chemical Reviews 88 (1988): 943-962.
Reza 52




18. S. F. Boys and F. Bernardi, “The calculation of small molecular interactions by the
differences of separate total energies. Some procedures with reduced errors,” Molecular
Physics 19 (1970): 553.
19. P. Hobza, J. Sponer, and T. J. Reschel. “Study in Gaussian,” Journal of
Computational Chemistry 11(1995): 1315.
20. Paul, J. B., Collier, C. P., Saykally, R. J., Scherer, J. J. and O’Keefe, “A Direct
measurement of water cluster concentrations by infrared cavity ring down laser
absorption spectroscopy,” Journal of Physical Chemistry A 101 (1997): 5211–5214.
21. I.M Svishchev and R.J Boyd, “van der Waals complexes of water with oxygen and
nitrogen: Infrared spectra and atmospheric implications,” Journal of Physical Chemistry
A 102 (1998): 7294–7296, accessed April 2012. doi:10.1021/jp981166d, 1998.
22. T. Tao, M. Higgins, and F. Nelson, “Structure, binding energy, and equilibrium
constant of the nitric acid-water complex,” Geophysics Review. Literature 23 (1996):
797–1800, accessed April 2012, doi: 10.1029/96GL00947.
23. H. G. Kjaergaard, T. W. Robinson, “High level ab initio studies of the low-lying
excited states in the H2O–O2complex,” Journal of Chemical Physics 119(2003): 3717-
3720.


Reza 53



24. Akiyoshi Sabu, Satomi Kondo, Ryu Saito, Yasuko Kasai, and Kenro Hashimoto,
“Theoretical Study of O 2-H2O: Potential Energy Surface, Molecular Vibrations, and
Equilibrium Constant at Atmospheric Temperatures,” Journal of Physical Chemistry A
109 (2005): 1836-1842.
25. J.E Headrick and V. Vaida, “Significance of water complexes in the atmosphere,”
Journal of Physical Chemistry 26 (2001): 479–486.
26. Y. Kasai, E. Dupuy, R. Saito,K. Hashimoto, A. Sabu, S. Kondo, Y. Sumiyoshi,
and Y. Endo, “The H2O-O2 water vapor complex in the Earth’s atmosphere,”
Atmospheric Chemical Physics 11 (2011): 8607–8612.
27. Pimentel, Whittle, and Dows, Journal of Chemical Physics 22, (1954): 1943.
28. I. R. Dunkin. Matrix Isolation Techniques: A Practical Approach. Oxford: Oxford
University Press, 1998.
29. Harimadhav Balu, “Species mobility and surface effects in matrix isolation
spectroscopy,” (Master’s thesis, Lamar University, 2005)
30. Prashanth Jayablu, “Determination of Wavenumbers of van der Waals Complexes
using Matrix Isolation Spectroscopy,” (Master’s thesis, Lamar University, 2005)
31. A. Frisch, R. D. Dennington II, T. A. Keith, A. B. Nielsen, A J. Holder. Gauss
View, Revision A.3, Pittsburgh, PA: Gaussian, Inc., 2003.
Reza 54



32. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R.
Cheeseman, V.G. Zakrzewski, Gaussian 03, Revision A.3,Pittsburgh PA :Gaussian, Inc.,
2003.
33. A. Frisch, R. D. Dennington II, T. A. Keith, A. B. Nielsen, A J. Holder, Gauss
View, Revision A.5, Pittsburgh PA: Gaussian, Inc., 2003.
34. S. Chin, T.A. Ford and W.B. Person, Journal of Molecular Structure, 113 (1984):
341.
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Physics 84 (1986):5687.
37. S. Chin and T.A. Ford, Journal of Molecular Structure 152 (1987): 363.
38. M. J. Brasler, V.C.E. Carr, M.G. Gerazounis, N.R. Jugga, G.A. Yeo and T.A.
Ford, Journal of Molecular Structure 180 (1988): 241.
39. T.D. Makomela Journal of Molecular Structure 275 (1992): 3&54.
40. G.A. Yeo and T.A. Ford, Journal of Molecular Structure 141 (1986): 331.
41. G.A. Yeo and T.A. Ford, S. Afr, Journal of Chemical Physics 39 (1986) 243.
42. F.M.M. O’Neill, G.A. Yeo and T.A. Ford, Journal of Molecular Structure 173
(1988): 337.
43. G.A. Yeo and T.A. Ford, Journal of Molecular Structure 168 (1988): 247.
Reza 55



44. D.G. Evans, G.A. Yeo and T.A. Ford, Faraday Discussion on Chemistry 86
(1988): 107.
45. G.A. Yeo and T.A. Ford, Journal of Molecular Structure 200 (1989): 507.

Reza 56



Appendix A
Gaussian Output file for Water-Nitrogen


Entering Link 1 = C:\G03W\l1.exe PID= 2516.

Copyright (c) 1988,1990,1992,1993,1995,1998,2003,2004, Gaussian, Inc.
All Rights Reserved.

This is the Gaussian(R) 03 program. It is based on the
the Gaussian(R) 98 system (copyright 1998, Gaussian, Inc.),
the Gaussian(R) 94 system (copyright 1995, Gaussian, Inc.),
the Gaussian 92(TM) system (copyright 1992, Gaussian, Inc.),
the Gaussian 90(TM) system (copyright 1990, Gaussian, Inc.),
the Gaussian 88(TM) system (copyright 1988, Gaussian, Inc.),
the Gaussian 86(TM) system (copyright 1986, Carnegie Mellon
University), and the Gaussian 82(TM) system (copyright 1983,
Carnegie Mellon University). Gaussian is a federally registered
trademark of Gaussian, Inc.

This software contains proprietary and confidential information,
including trade secrets, belonging to Gaussian, Inc.

This software is provided under written license and may be
used, copied, transmitted, or stored only in accord with that
written license.

The following legend is applicable only to US Government
contracts under FAR:

RESTRICTED RIGHTS LEGEND

Use, reproduction and disclosure by the US Government is
subject to restrictions as set forth in subparagraphs (a)
and (c) of the Commercial Computer Software - Restricted
Rights clause in FAR 52.227-19.

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340 Quinnipiac St., Bldg. 40, Wallingford CT 06492


---------------------------------------------------------------
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competes with the business of Gaussian, Inc. or will provide
assistance to any competitor of Gaussian, Inc. The licensee
of this program is prohibited from giving any competitor of
Gaussian, Inc. access to this program. By using this program,
the user acknowledges that Gaussian, Inc. is engaged in the
business of creating and licensing software in the field of
computational chemistry and represents and warrants to the
licensee that it is not a competitor of Gaussian, Inc. and that
it will not use this program in any manner prohibited above.
---------------------------------------------------------------


Cite this work as:
Reza 57



Gaussian 03, Revision C.02,
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven,
K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega,
G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota,
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala,
K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg,
V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain,
O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari,
J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford,
J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,
I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham,
C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill,
B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople,
Gaussian, Inc., Wallingford CT, 2004.

******************************************
Gaussian 03: IA32W-G03RevC.02 12-Jun-2004
02-Jul-2012
******************************************
%chk=en4.chk
%mem=6MW
%nproc=1
Will use up to 1 processors via shared memory.
----------------------------------------------
# opt rb3lyp/6-311++g(2d,2p) geom=connectivity
----------------------------------------------
1/14=-1,18=20,26=3,38=1,57=2/1,3;
2/9=110,17=6,18=5,40=1/2;
3/5=4,6=6,7=1212,11=2,16=1,25=1,30=1,74=-5/1,2,3;
4/7=1/1;
5/5=2,38=5/2;
6/7=2,8=2,9=2,10=2,28=1/1;
7//1,2,3,16;
1/14=-1,18=20/3(1);
99//99;
2/9=110/2;
3/5=4,6=6,7=1212,11=2,16=1,25=1,30=1,74=-5/1,2,3;
4/5=5,7=1,16=3/1;
5/5=2,38=5/2;
7//1,2,3,16;
1/14=-1,18=20/3(-5);
2/9=110/2;
6/7=2,8=2,9=2,10=2,19=2,28=1/1;
99/9=1/99;
-------------------
Title Card Required
-------------------
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
O
H 1 B1
H 1 B2 2 A1
Reza 58



N 1 B3 2 A2 3 D1 0
N 2 B4 1 A3 4 D2 0
Variables:
B1 0.958
B2 0.958
B3 3.291
B4 4.73264
A1 104.5
A2 104.5
A3 64.19823
D1 0.
D2 0.



GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Initialization pass.
----------------------------
! Initial Parameters !
! (Angstroms and Degrees) !
-------------------------- ----------------
----------
! Name Definition Value Derivative Info.
!
----------------------------------------------------------------------
----------
! R1 R(1,2) 0.958 estimate D2E/DX2
!
! R2 R(1,3) 0.958 estimate D2E/DX2
!
! R3 R(3,4) 2.333 estimate D2E/DX2
!
! R4 R(4,5) 1.11 estimate D2E/DX2
!
! A1 A(2,1,3) 104.5 estimate D2E/DX2
!
! A2 L(3,4,5,-2,-1) 180.0 estimate D2E/DX2
!
! A3 L(3,4,5,-3,-2) 180.0 estimate D2E/DX2
!
! A4 L(1,3,4,2,-1) 180.0 estimate D2E/DX2
!
! A5 L(1,3,4,2,-2) 180.0 estimate D2E/DX2
!
----------------------------------------------------------------------
----------
Trust Radius=3.00D-01 FncErr=1.00D-07 GrdErr=1.00D-06
Number of steps in this run= 20 maximum allowed number of steps= 100.

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Reza 59



Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.000000 0.000000 0.000000
2 1 0 0.000000 0.000000 0.958000
3 1 0 0.927485 0.000000 -0.239864
4 7 0 3.186174 0.000000 -0.824001
5 7 0 4.260818 0.000000 -1.101923
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.958000 0.000000
3 H 0.958000 1.514961 0.000000
4 N 3.291000 3.650648 2.333000 0.000000
5 N 4.401000 4.732636 3.443000 1.110000 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.038645 2.273422 0.000000
2 1 0 -0.888840 2.513286 0.000000
3 1 0 0.038645 1.315422 0.000000
4 7 0 0.038645 -1.017578 0.000000
5 7 0 0.038645 -2.127578 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 621.7622919 3.0013718
2.9869531
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.7464134128 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Reza 60



Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A") (A') (A') (A") (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A') (A')
(A') (A") (A') (A') (A') (A") (A") (A') (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A") (A') (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
The electronic state of the initial guess is 1-A'.
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.025773347 A.U. after 10 cycles
Convg = 0.4338D-08 -V/T = 2.0036
S**2 = 0.0000

**********************************************************************

Population analysis using the SCF density.

**********************************************************************

Orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A") (A') (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
The electronic state is 1-A'.
Alpha occ. eigenvalues -- -19.12558 -14.44371 -14.44204 -1.14548 -
1.01651
Alpha occ. eigenvalues -- -0.58479 -0.53480 -0.48657 -0.48646 -
0.45904
Alpha occ. eigenvalues -- -0.39278 -0.31713
Alpha virt. eigenvalues -- -0.05968 -0.05926 -0.01081 0.03475
0.06677
Alpha virt. eigenvalues -- 0.08062 0.08295 0.12029 0.12320
0.14329
Alpha virt. eigenvalues -- 0.15724 0.16298 0.19004 0.20679
0.23477
Alpha virt. eigenvalues -- 0.26211 0.29693 0.37811 0.51711
0.53348
Alpha virt. eigenvalues -- 0.58713 0.67185 0.68628 0.68804
0.69872
Alpha virt. eigenvalues -- 0.73130 0.73942 0.78507 0.79396
0.79408
Alpha virt. eigenvalues -- 0.80022 0.83662 0.88210 0.92298
0.97245
Reza 61



Alpha virt. eigenvalues -- 1.00529 1.02334 1.07663 1.09260
1.21479
Alpha virt. eigenvalues -- 1.21485 1.22040 1.31490 1.40132
1.55202
Alpha virt. eigenvalues -- 1.71388 1.72340 1.77701 1.81390
1.89021
Alpha virt. eigenvalues -- 1.91296 1.98397 2.21486 2.34981
2.57800
Alpha virt. eigenvalues -- 2.98502 3.62544 3.62839 3.72270
3.72891
Alpha virt. eigenvalues -- 3.74227 3.90958 3.92162 3.95107
3.99704
Alpha virt. eigenvalues -- 4.13863 4.30475 4.37135 4.37671
4.42604
Alpha virt. eigenvalues -- 4.57494 4.57501 4.72669 4.72681
4.74605
Alpha virt. eigenvalues -- 5.00768 5.17552 5.17622 5.59157
6.15028
Alpha virt. eigenvalues -- 6.19876 6.85749 6.87647 7.00651
7.28325
Alpha virt. eigenvalues -- 7.50343 35.09806 35.90074 49.90774
Condensed to atoms (all electrons):
1 2 3 4 5
1 O 7.965964 0.264231 0.279674 -0.001328 0.013224
2 H 0.264231 0.515682 -0.011086 0.000118 -0.000723
3 H 0.279674 -0.011086 0.394741 0.014208 0.015460
4 N -0.001328 0.000118 0.014208 6.448600 0.655911
5 N 0.013224 -0.000723 0.015460 0.655911 6.215637
Mulliken atomic charges:
1
1 O -0.521765
2 H 0.231779
3 H 0.307005
4 N -0.117509
5 N 0.100491
Sum of Mulliken charges= 0.00000
Atomic charges with hydrogens summed into heavy atoms:
1
1 O 0.017018
2 H 0.000000
3 H 0.000000
4 N -0.117509
5 N 0.100491
Sum of Mulliken charges= 0.00000
Electronic spatial extent (au): <R**2>= 360.1588
Charge= 0.0000 electrons
Dipole moment (field-independent basis, Debye):
X= -1.5244 Y= -1.5028 Z= 0.0000 Tot= 2.1406
Quadrupole moment (field-independent basis, Debye-Ang):
XX= -15.9129 YY= -22.1319 ZZ= -18.1597
XY= -4.3382 XZ= 0.0000 YZ= 0.0000
Traceless Quadrupole moment (field-independent basis, Debye-Ang):
XX= 2.8220 YY= -3.3971 ZZ= 0.5751
XY= -4.3382 XZ= 0.0000 YZ= 0.0000
Octapole moment (field-independent basis, Debye-Ang**2):
XXX= -2.0281 YYY= -0.4949 ZZZ= 0.0000 XYY= -11.8200
XXY= 4.2647 XXZ= 0.0000 XZZ= -0.2427 YZZ= -1.2095
Reza 62



YYZ= 0.0000 XYZ= 0.0000
Hexadecapole moment (field-independent basis, Debye-Ang**3):
XXXX= -16.0162 YYYY= -433.0531 ZZZZ= -16.7632 XXXY= -0.5320
XXXZ= 0.0000 YYYX= -27.4332 YYYZ= 0.0000 ZZZX= 0.0000
ZZZY= 0.0000 XXYY= -60.1234 XXZZ= -5.7307 YYZZ= -73.4640
XXYZ= 0.0000 YYXZ= 0.0000 ZZXY= 0.9678
N-N= 5.274641341277D+01 E-N=-5.426420332566D+02 KE=
1.853574064744D+02
Symmetry A' KE= 1.773928988873D+02
Symmetry A" KE= 7.964507587084D+00
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.002521615 0.000000000 -0.000760950
2 1 -0.001352889 0.000000000 0.003002776
3 1 0.003364963 0.000000000 -0.002108960
4 7 0.051798368 0.000000000 -0.013263444
5 7 -0.051288828 0.000000000 0.013130578
-------------------------------------------------------------------
Cartesian Forces: Max 0.051798368 RMS 0.019485894


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.052942793 RMS 0.017754432
Search for a local minimum.
Step number 1 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Second derivative matrix not updated -- first step.
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.55906
R2 0.00000 0.55906
R3 0.00000 0.00000 0.02597
R4 0.00000 0.00000 0.00000 1.67009
A1 0.00000 0.00000 0.00000 0.00000 0.16000
A2 0.00000 0.00000 0.00000 0.00000 0.00000
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 0.00000 0.00000 0.00000 0.00000 0.00000
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.16000
A3 0.00000 0.16000
A4 0.00000 0.00000 0.25000
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.02597 0.16000 0.16000 0.16000 0.25000
Eigenvalues --- 0.25000 0.55906 0.55906 1.67009
RFO step: Lambda=-1.77359680D-03.
Linear search not attempted -- first point.
Iteration 1 RMS(Cart)= 0.01353528 RMS(Int)= 0.00007395
Iteration 2 RMS(Cart)= 0.00005762 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
Reza 63



R1 1.81036 0.00300 0.00000 0.00535 0.00535 1.81571
R2 1.81036 0.00431 0.00000 0.00769 0.00769 1.81805
R3 4.40873 0.00053 0.00000 0.01898 0.01898 4.42771
R4 2.09760 -0.05294 0.00000 -0.03167 -0.03167 2.06593
A1 1.82387 0.00245 0.00000 0.01514 0.01514 1.83901
A2 3.14159 -0.00027 0.00000 -0.00168 -0.00168 3.13992
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.14159 0.00028 0.00000 0.00110 0.00110 3.14269
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.052943 0.000450 NO
RMS Force 0.017754 0.000300 NO
Maximum Displacement 0.027360 0.001800 NO
RMS Displacement 0.013539 0.001200 NO
Predicted change in Energy=-8.882943D-04

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.000262 0.000000 0.001476
2 1 0 -0.014478 0.000000 0.962196
3 1 0 0.931736 0.000000 -0.239218
4 7 0 3.199622 0.000000 -0.827897
5 7 0 4.257335 0.000000 -1.104344
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960833 0.000000
3 H 0.962069 1.529286 0.000000
4 N 3.305111 3.678977 2.343043 0.000000
5 N 4.398352 4.745416 3.436284 1.093243 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.121959 -2.273338 0.000000
2 1 0 0.794269 -2.562693 0.000000
3 1 0 -0.085711 -1.311952 0.000000
4 7 0 0.000000 1.029522 0.000000
5 7 0 0.038159 2.122099 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 624.1920946 2.9961732
2.9818600
Standard basis: 6-311++G(2d,2p) (5D, 7F)
Reza 64



There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 53.0204714299 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A") (A') (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026779802 A.U. after 11 cycles
Convg = 0.3506D-08 -V/T = 2.0032
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000007664 0.000000000 -0.000077512
2 1 0.000198296 0.000000000 -0.000346431
3 1 -0.000602930 0.000000000 0.000532157
4 7 0.006854763 0.000000000 -0.001664490
5 7 -0.006457793 0.000000000 0.001556276
-------------------------------------------------------------------
Cartesian Forces: Max 0.006854763 RMS 0.002512575


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Reza 65



Internal Forces: Max 0.006641544 RMS 0.002230522
Search for a local minimum.
Step number 2 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2
Trust test= 1.13D+00 RLast= 4.10D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.56118
R2 0.00263 0.56226
R3 -0.00059 -0.00086 0.02584
R4 -0.00979 -0.00830 0.01131 1.46092
A1 0.00191 0.00239 -0.00047 -0.01055 0.16170
A2 0.00044 0.00064 0.00007 -0.00785 0.00036
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00051 -0.00073 -0.00008 0.00883 -0.00041
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.15996
A3 0.00000 0.16000
A4 0.00004 0.00000 0.24996
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.02575 0.15986 0.16000 0.16164 0.24989
Eigenvalues --- 0.25000 0.55903 0.56425 1.46139
RFO step: Lambda=-1.03469528D-05.
Quartic linear search produced a step of 0.12562.
Iteration 1 RMS(Cart)= 0.00355763 RMS(Int)= 0.00000205
Iteration 2 RMS(Cart)= 0.00000222 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81571 -0.00035 0.00067 -0.00142 -0.00074 1.81497
R2 1.81805 -0.00031 0.00097 -0.00164 -0.00068 1.81737
R3 4.42771 0.00041 0.00238 0.00981 0.01219 4.43990
R4 2.06593 -0.00664 -0.00398 -0.00055 -0.00452 2.06141
A1 1.83901 -0.00035 0.00190 -0.00502 -0.00312 1.83589
A2 3.13992 -0.00027 -0.00021 -0.00159 -0.00180 3.13812
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.14269 0.00030 0.00014 0.00118 0.00131 3.14400
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.006642 0.000450 NO
RMS Force 0.002231 0.000300 NO
Maximum Displacement 0.007492 0.001800 NO
RMS Displacement 0.003557 0.001200 NO
Predicted change in Energy=-1.997916D-05

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.002010 0.000000 0.001624
2 1 0 -0.015033 0.000000 0.961975
Reza 66



3 1 0 0.929439 0.000000 -0.237733
4 7 0 3.203587 0.000000 -0.827972
5 7 0 4.258493 0.000000 -1.105683
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960439 0.000000
3 H 0.961711 1.526868 0.000000
4 N 3.311205 3.682855 2.349496 0.000000
5 N 4.402046 4.747445 3.440340 1.090849 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.119738 -2.276377 0.000000
2 1 0 0.796958 -2.562930 0.000000
3 1 0 -0.083318 -1.315356 0.000000
4 7 0 0.000000 1.032662 0.000000
5 7 0 0.034895 2.122953 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 624.3821144 2.9897165
2.9754692
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 53.0473528060 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
Reza 67



(A') (A") (A") (A') (A') (A') (A') (A') (A')
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026799874 A.U. after 8 cycles
Convg = 0.3555D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.000041808 0.000000000 -0.000173430
2 1 -0.000098591 0.000000000 0.000146099
3 1 -0.000218385 0.000000000 0.000122570
4 7 -0.000043177 0.000000000 0.000141900
5 7 0.000401961 0.000000000 -0.000237139
-------------------------------------------------------------------
Cartesian Forces: Max 0.000401961 RMS 0.000156080


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000449003 RMS 0.000249021
Search for a local minimum.
Step number 3 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3
Trust test= 1.00D+00 RLast= 1.36D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.56321
R2 0.00407 0.56324
R3 0.00128 0.00075 0.02418
R4 0.01881 0.01169 0.05341 1.73955
A1 0.00362 0.00355 0.00194 0.00954 0.16296
A2 -0.00177 -0.00123 0.00166 -0.05558 -0.00239
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 0.00186 0.00128 -0.00189 0.06062 0.00256
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.15849
A3 0.00000 0.16000
A4 0.00173 0.00000 0.24802
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.02234 0.15585 0.16000 0.16343 0.24585
Eigenvalues --- 0.25000 0.55913 0.56696 1.74608
RFO step: Lambda=-6.77342599D-06.
Quartic linear search produced a step of 0.07410.
Iteration 1 RMS(Cart)= 0.00656748 RMS(Int)= 0.00000214
Iteration 2 RMS(Cart)= 0.00000205 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
Reza 68



R1 1.81497 0.00015 -0.00006 0.00028 0.00022 1.81519
R2 1.81737 0.00013 -0.00005 0.00025 0.00020 1.81757
R3 4.43990 0.00037 0.00090 0.01535 0.01626 4.45616
R4 2.06141 0.00045 -0.00034 -0.00002 -0.00036 2.06105
A1 1.83589 0.00017 -0.00023 0.00107 0.00084 1.83673
A2 3.13812 -0.00026 -0.00013 -0.00183 -0.00196 3.13615
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.14400 0.00028 0.00010 0.00126 0.00135 3.14536
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000449 0.000450 YES
RMS Force 0.000249 0.000300 YES
Maximum Displacement 0.010557 0.001800 NO
RMS Displacement 0.006566 0.001200 NO
Predicted change in Energy=-3.496192D-06

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.004967 0.000000 0.002558
2 1 0 -0.019856 0.000000 0.962999
3 1 0 0.926848 0.000000 -0.235799
4 7 0 3.209173 0.000000 -0.828774
5 7 0 4.263278 0.000000 -1.108771
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960556 0.000000
3 H 0.961817 1.527535 0.000000
4 N 3.319911 3.692841 2.358098 0.000000
5 N 4.410552 4.757885 3.448746 1.090659 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.117302 -2.281451 0.000000
2 1 0 0.799226 -2.568930 0.000000
3 1 0 -0.080749 -1.320328 0.000000
4 7 0 0.000000 1.036387 0.000000
5 7 0 0.031420 2.126593 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 625.3329504 2.9768837
2.9627795
Standard basis: 6-311++G(2d,2p) (5D, 7F)
Reza 69



There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 53.0010612909 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026806194 A.U. after 8 cycles
Convg = 0.2011D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000001599 0.000000000 -0.000150314
2 1 -0.000010022 0.000000000 0.000006638
3 1 -0.000300409 0.000000000 0.000224825
4 7 -0.000653974 0.000000000 0.000302698
5 7 0.000962806 0.000000000 -0.000383848
-------------------------------------------------------------------
Cartesian Forces: Max 0.000962806 RMS 0.000342265


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.001029000 RMS 0.000380283
Search for a local minimum.
Step number 4 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4
Reza 70



Trust test= 1.81D+00 RLast= 1.65D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57466
R2 0.01749 0.57872
R3 -0.00116 -0.00010 0.00673
R4 -0.06025 -0.07647 0.01087 2.23106
A1 0.01510 0.01708 -0.00113 -0.07786 0.17459
A2 0.00174 0.00130 0.01539 -0.04165 0.00189
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00131 -0.00074 -0.01639 0.04182 -0.00135
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.14835
A3 0.00000 0.16000
A4 0.01261 0.00000 0.23636
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00357 0.14774 0.16000 0.17077 0.23837
Eigenvalues --- 0.25000 0.55906 0.58934 2.24160
RFO step: Lambda=-3.71049783D-06.
Quartic linear search produced a step of 2.00000.
Iteration 1 RMS(Cart)= 0.01846779 RMS(Int)= 0.00002041
Iteration 2 RMS(Cart)= 0.00002023 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81519 0.00001 0.00044 -0.00032 0.00013 1.81531
R2 1.81757 -0.00003 0.00040 -0.00044 -0.00003 1.81754
R3 4.45616 0.00032 0.03251 0.01356 0.04607 4.50223
R4 2.06105 0.00103 -0.00072 0.00076 0.00004 2.06109
A1 1.83673 0.00002 0.00168 -0.00122 0.00046 1.83719
A2 3.13615 -0.00026 -0.00392 -0.00283 -0.00675 3.12940
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.14536 0.00027 0.00271 0.00192 0.00463 3.14999
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.001029 0.000450 NO
RMS Force 0.000380 0.000300 NO
Maximum Displacement 0.029448 0.001800 NO
RMS Displacement 0.018455 0.001200 NO
Predicted change in Energy=-1.334714D-05

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.013543 0.000000 0.004880
2 1 0 -0.032734 0.000000 0.965311
3 1 0 0.919204 0.000000 -0.229728
4 7 0 3.224756 0.000000 -0.830247
5 7 0 4.276794 0.000000 -1.118005
---------------------------------------------------------------------
Distance matrix (angstroms):
Reza 71



1 2 3 4 5
1 O 0.000000
2 H 0.960623 0.000000
3 H 0.961799 1.527843 0.000000
4 N 3.344252 3.719580 2.382477 0.000000
5 N 4.434846 4.786673 3.473103 1.090682 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.109104 -2.295865 0.000000
2 1 0 0.807183 -2.584333 0.000000
3 1 0 -0.071979 -1.334782 0.000000
4 7 0 0.000000 1.046607 0.000000
5 7 0 0.019661 2.137112 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 627.7825773 2.9410044
2.9272908
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.8629872058 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
Reza 72



ScaDFX= 1.000000 1.000000 1.000000 1.000000
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026820593 A.U. after 8 cycles
Convg = 0.9260D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.000008807 0.000000000 -0.000133005
2 1 0.000051227 0.000000000 -0.000064235
3 1 -0.000223854 0.000000000 0.000242230
4 7 -0.000749227 0.000000000 0.000327183
5 7 0.000930662 0.000000000 -0.000372173
-------------------------------------------------------------------
Cartesian Forces: Max 0.000930662 RMS 0.000347020


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000995813 RMS 0.000358680
Search for a local minimum.
Step number 5 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4 5

Trust test= 1.08D+00 RLast= 4.68D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57110
R2 0.01243 0.57176
R3 0.00005 0.00148 0.00765
R4 -0.00158 -0.00274 -0.00990 1.67772
A1 0.01090 0.01113 0.00086 -0.01756 0.17007
A2 0.00077 -0.00037 0.01891 -0.03675 0.00113
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00034 0.00091 -0.01991 0.03790 -0.00049
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.14404
A3 0.00000 0.16000
A4 0.01741 0.00000 0.23106
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00292 0.14300 0.16000 0.16931 0.23487
Eigenvalues --- 0.25000 0.55900 0.58443 1.67986
RFO step: Lambda=-1.50793914D-06.
Quartic linear search produced a step of 2.00000.
Iteration 1 RMS(Cart)= 0.03725458 RMS(Int)= 0.00009490
Iteration 2 RMS(Cart)= 0.00009491 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
Reza 73



(Linear) (Quad) (Total)
R1 1.81531 -0.00006 0.00025 -0.00032 -0.00007 1.81524
R2 1.81754 -0.00009 -0.00007 -0.00034 -0.00040 1.81713
R3 4.50223 0.00019 0.09214 0.00114 0.09328 4.59551
R4 2.06109 0.00100 0.00009 0.00049 0.00058 2.06167
A1 1.83719 -0.00009 0.00092 -0.00171 -0.00079 1.83640
A2 3.12940 -0.00024 -0.01350 -0.00149 -0.01499 3.11441
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.14999 0.00023 0.00926 0.00084 0.01010 3.16009
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000996 0.000450 NO
RMS Force 0.000359 0.000300 NO
Maximum Displacement 0.059484 0.001800 NO
RMS Displacement 0.037193 0.001200 NO
Predicted change in Energy=-1.032477D-05

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.031030 0.000000 0.009244
2 1 0 -0.058114 0.000000 0.969448
3 1 0 0.903585 0.000000 -0.216899
4 7 0 3.256234 0.000000 -0.832428
5 7 0 4.303802 0.000000 -1.137152
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960586 0.000000
3 H 0.961585 1.527182 0.000000
4 N 3.393305 3.772487 2.431838 0.000000
5 N 4.483859 4.843973 3.522547 1.090988 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.091241 -2.324898 0.000000
2 1 0 0.824795 -2.614040 0.000000
3 1 0 -0.052647 -1.364088 0.000000
4 7 0 0.000000 1.067180 0.000000
5 7 0 -0.006031 2.158151 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 630.5914958 2.8706372
2.8576284
Reza 74



Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.5868314465 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A")
(A') (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026832787 A.U. after 9 cycles
Convg = 0.9620D-09 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.000060947 0.000000000 -0.000104779
2 1 0.000005848 0.000000000 0.000015161
3 1 0.000086572 0.000000000 0.000074809
4 7 -0.000156203 0.000000000 0.000146235
5 7 0.000124730 0.000000000 -0.000131425
-------------------------------------------------------------------
Cartesian Forces: Max 0.000156203 RMS 0.000084326


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Reza 75



Berny optimization.
Internal Forces: Max 0.000190190 RMS 0.000100732
Search for a local minimum.
Step number 6 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4 5
6
Trust test= 1.18D+00 RLast= 9.50D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57187
R2 0.01324 0.57260
R3 -0.00074 0.00026 0.00792
R4 0.00525 0.00723 -0.00261 1.55393
A1 0.01076 0.01071 0.00029 -0.00136 0.16915
A2 -0.00142 -0.00345 0.02027 -0.00768 -0.00107
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 0.00180 0.00392 -0.02097 0.00702 0.00169
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.14213
A3 0.00000 0.16000
A4 0.01942 0.00000 0.22899
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00244 0.14210 0.16000 0.16862 0.23431
Eigenvalues --- 0.25000 0.55900 0.58602 1.55410
RFO step: Lambda=-4.11386990D-07.
Quartic linear search produced a step of 0.07414.
Iteration 1 RMS(Cart)= 0.00302460 RMS(Int)= 0.00000228
Iteration 2 RMS(Cart)= 0.00000235 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81524 0.00002 -0.00001 0.00003 0.00003 1.81527
R2 1.81713 0.00003 -0.00003 0.00006 0.00003 1.81716
R3 4.59551 -0.00003 0.00692 -0.00067 0.00625 4.60175
R4 2.06167 0.00016 0.00004 0.00005 0.00009 2.06176
A1 1.83640 -0.00001 -0.00006 -0.00006 -0.00012 1.83628
A2 3.11441 -0.00019 -0.00111 -0.00132 -0.00243 3.11198
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.16009 0.00017 0.00075 0.00076 0.00151 3.16160
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000190 0.000450 YES
RMS Force 0.000101 0.000300 YES
Maximum Displacement 0.004610 0.001800 NO
RMS Displacement 0.003023 0.001200 NO
Predicted change in Energy=-2.504717D-07

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
Reza 76



1 8 0 -0.032103 0.000000 0.009334
2 1 0 -0.060479 0.000000 0.969514
3 1 0 0.902856 0.000000 -0.215447
4 7 0 3.258674 0.000000 -0.831926
5 7 0 4.305529 0.000000 -1.139262
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960599 0.000000
3 H 0.961600 1.527137 0.000000
4 N 3.396606 3.776501 2.435143 0.000000
5 N 4.487129 4.848604 3.525850 1.091037 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.088428 -2.326869 0.000000
2 1 0 0.827587 -2.616121 0.000000
3 1 0 -0.049611 -1.366053 0.000000
4 7 0 0.000000 1.068585 0.000000
5 7 0 -0.010079 2.159576 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 630.7173411 2.8659548
2.8529909
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.5675196545 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
Reza 77



(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026833229 A.U. after 8 cycles
Convg = 0.3313D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.000032810 0.000000000 -0.000091257
2 1 -0.000001046 0.000000000 0.000006591
3 1 0.000078373 0.000000000 0.000067061
4 7 -0.000035112 0.000000000 0.000106264
5 7 -0.000009405 0.000000000 -0.000088659
-------------------------------------------------------------------
Cartesian Forces: Max 0.000106264 RMS 0.000052001


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000182670 RMS 0.000083379
Search for a local minimum.
Step number 7 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4 5
6 7
Trust test= 1.77D+00 RLast= 6.87D-03 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57286
R2 0.01459 0.57475
R3 0.00100 0.00415 0.00807
R4 0.00747 0.01599 0.02478 1.59744
A1 0.01087 0.01014 -0.00202 -0.01279 0.17056
A2 0.00339 0.00660 0.00923 0.04316 -0.00495
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00256 -0.00520 -0.01145 -0.03868 0.00527
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.07665
A3 0.00000 0.16000
A4 0.07720 0.00000 0.17803
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00229 0.03768 0.16000 0.17016 0.21980
Eigenvalues --- 0.25000 0.55918 0.58882 1.60045
RFO step: Lambda=-1.33705601D-06.
Quartic linear search produced a step of 2.00000.
Iteration 1 RMS(Cart)= 0.00715446 RMS(Int)= 0.00002949
Iteration 2 RMS(Cart)= 0.00003069 RMS(Int)= 0.00000000
Reza 78



Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81527 0.00001 0.00005 0.00002 0.00007 1.81534
R2 1.81716 0.00001 0.00006 0.00005 0.00011 1.81727
R3 4.60175 -0.00005 0.01249 -0.00390 0.00859 4.61034
R4 2.06176 0.00002 0.00018 0.00006 0.00024 2.06200
A1 1.83628 0.00000 -0.00023 -0.00008 -0.00031 1.83597
A2 3.11198 -0.00018 -0.00487 -0.00402 -0.00889 3.10309
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.16160 0.00016 0.00302 0.00234 0.00536 3.16696
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000183 0.000450 YES
RMS Force 0.000083 0.000300 YES
Maximum Displacement 0.011553 0.001800 NO
RMS Displacement 0.007142 0.001200 NO
Predicted change in Energy=-1.174459D-06

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.033111 0.000000 0.008673
2 1 0 -0.066344 0.000000 0.968736
3 1 0 0.903096 0.000000 -0.211102
4 7 0 3.263315 0.000000 -0.828719
5 7 0 4.307522 0.000000 -1.145376
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960638 0.000000
3 H 0.961657 1.527034 0.000000
4 N 3.401124 3.783843 2.439689 0.000000
5 N 4.491428 4.858001 3.530295 1.091165 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.078244 -2.329602 0.000000
2 1 0 0.837660 -2.619336 0.000000
3 1 0 -0.038635 -1.368761 0.000000
4 7 0 0.000000 1.070623 0.000000
5 7 0 -0.024725 2.161507 0.000000
---------------------------------------------------------------------
Reza 79



Rotational constants (GHZ): 630.5641231 2.8594706
2.8465620
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.5388563052 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026834982 A.U. after 9 cycles
Convg = 0.4500D-09 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000051140 0.000000000 -0.000051452
2 1 -0.000021114 0.000000000 -0.000021260
3 1 0.000034157 0.000000000 0.000054041
4 7 0.000302890 0.000000000 -0.000015018
5 7 -0.000367074 0.000000000 0.000033689
-------------------------------------------------------------------
Cartesian Forces: Max 0.000367074 RMS 0.000125988


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000361085 RMS 0.000143883
Search for a local minimum.
Reza 80



Step number 8 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4 5
6 7 8
Trust test= 1.49D+00 RLast= 1.35D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57561
R2 0.01960 0.58422
R3 0.00278 0.00716 0.00545
R4 0.03873 0.07787 0.04221 1.99823
A1 0.00880 0.00587 -0.00258 -0.04267 0.17271
A2 0.00330 0.00559 0.00128 0.03082 -0.00255
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00347 -0.00640 -0.00526 -0.04118 0.00441
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.06080
A3 0.00000 0.16000
A4 0.09190 0.00000 0.16490
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00243 0.00793 0.16000 0.17134 0.21838
Eigenvalues --- 0.25000 0.55959 0.59537 2.00687
RFO step: Lambda=-3.26873216D-06.
Quartic linear search produced a step of 2.00000.
Iteration 1 RMS(Cart)= 0.01788576 RMS(Int)= 0.00026292
Iteration 2 RMS(Cart)= 0.00027640 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000001 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81534 -0.00002 0.00015 0.00002 0.00017 1.81551
R2 1.81727 -0.00005 0.00022 0.00005 0.00026 1.81753
R3 4.61034 -0.00007 0.01718 -0.01553 0.00165 4.61200
R4 2.06200 -0.00036 0.00048 0.00002 0.00050 2.06250
A1 1.83597 0.00004 -0.00062 0.00017 -0.00044 1.83553
A2 3.10309 -0.00015 -0.01777 -0.00890 -0.02667 3.07642
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.16696 0.00015 0.01072 0.00521 0.01593 3.18289
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000361 0.000450 YES
RMS Force 0.000144 0.000300 YES
Maximum Displacement 0.029466 0.001800 NO
RMS Displacement 0.017859 0.001200 NO
Predicted change in Energy=-3.462857D-06

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.030941 0.000000 0.005017
2 1 0 -0.079309 0.000000 0.964527
3 1 0 0.908840 0.000000 -0.199588
Reza 81



4 7 0 3.270075 0.000000 -0.816776
5 7 0 4.305812 0.000000 -1.160968
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960728 0.000000
3 H 0.961796 1.526958 0.000000
4 N 3.401772 3.793602 2.440564 0.000000
5 N 4.490763 4.873091 3.530393 1.091430 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.047797 -2.329763 0.000000
2 1 0 0.867602 -2.621386 0.000000
3 1 0 -0.005806 -1.368884 0.000000
4 7 0 0.000000 1.071673 0.000000
5 7 0 -0.068488 2.160952 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 624.3623541 2.8585607
2.8455328
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.5259194537 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A") (A') (A') (A')
(A") (A') (A') (A") (A') (A") (A') (A") (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Reza 82



Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026839608 A.U. after 9 cycles
Convg = 0.1486D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000216874 0.000000000 0.000033691
2 1 -0.000047754 0.000000000 -0.000096442
3 1 -0.000092286 0.000000000 0.000056212
4 7 0.001027145 0.000000000 -0.000324453
5 7 -0.001103979 0.000000000 0.000330992
-------------------------------------------------------------------
Cartesian Forces: Max 0.001103979 RMS 0.000413122


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.001152040 RMS 0.000395399
Search for a local minimum.
Step number 9 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4 5
6 7 8 9
Trust test= 1.34D+00 RLast= 3.11D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.58149
R2 0.02915 0.59962
R3 0.00320 0.00721 0.00360
R4 0.07010 0.12282 0.02602 1.98440
A1 0.00759 0.00428 -0.00107 -0.03408 0.17183
A2 0.00048 0.00014 -0.00140 -0.00560 0.00043
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00361 -0.00610 -0.00315 -0.02854 0.00300
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.05975
A3 0.00000 0.16000
A4 0.09516 0.00000 0.16167
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00258 0.00326 0.16000 0.17080 0.21836
Eigenvalues --- 0.25000 0.55981 0.60719 2.00035
RFO step: Lambda=-5.39916053D-06.
Quartic linear search produced a step of 2.00000.
Reza 83



Iteration 1 RMS(Cart)= 0.04310160 RMS(Int)= 0.00157085
Iteration 2 RMS(Cart)= 0.00166953 RMS(Int)= 0.00000021
Iteration 3 RMS(Cart)= 0.00000029 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81551 -0.00009 0.00034 -0.00014 0.00020 1.81571
R2 1.81753 -0.00018 0.00052 -0.00027 0.00026 1.81779
R3 4.61200 -0.00008 0.00331 -0.01447 -0.01116 4.60083
R4 2.06250 -0.00115 0.00100 -0.00108 -0.00008 2.06243
A1 1.83553 0.00009 -0.00088 0.00080 -0.00008 1.83545
A2 3.07642 -0.00007 -0.05335 -0.01169 -0.06504 3.01138
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.18289 0.00014 0.03186 0.00732 0.03918 3.22207
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.001152 0.000450 NO
RMS Force 0.000395 0.000300 NO
Maximum Displacement 0.066959 0.001800 NO
RMS Displacement 0.043161 0.001200 NO
Predicted change in Energy=-2.440442D-06

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.020845 0.000000 -0.004996
2 1 0 -0.107297 0.000000 0.951939
3 1 0 0.926470 0.000000 -0.172059
4 7 0 3.282376 0.000000 -0.786272
5 7 0 4.293773 0.000000 -1.196402
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960832 0.000000
3 H 0.961933 1.527104 0.000000
4 N 3.394357 3.809365 2.434657 0.000000
5 N 4.476089 4.897426 3.519660 1.091389 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.026043 -2.321845 0.000000
2 1 0 0.939695 -2.619232 0.000000
3 1 0 0.074138 -1.361115 0.000000
4 7 0 0.000000 1.072413 0.000000
Reza 84



5 7 0 -0.174597 2.149745 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 577.0133334 2.8727743
2.8585425
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.5654104592 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A") (A') (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A') (A") (A') (A") (A") (A') (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026843154 A.U. after 10 cycles
Convg = 0.2364D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000348490 0.000000000 0.000128416
2 1 -0.000039239 0.000000000 -0.000193765
3 1 -0.000233157 0.000000000 0.000098333
4 7 0.000870310 0.000000000 -0.000485745
5 7 -0.000946404 0.000000000 0.000452760
-------------------------------------------------------------------
Cartesian Forces: Max 0.000946404 RMS 0.000394556
Reza 85





GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.001047128 RMS 0.000376678
Search for a local minimum.
Step number 10 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 1 2 3 4 5
6 7 8 9 10
Trust test= 1.45D+00 RLast= 7.67D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.58709
R2 0.03715 0.61082
R3 0.00278 0.00614 0.00292
R4 0.04769 0.07795 0.00752 1.60803
A1 0.00957 0.00788 0.00004 -0.00704 0.17033
A2 -0.00242 -0.00444 -0.00189 -0.00833 0.00108
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 -0.00387 -0.00615 -0.00262 -0.01193 0.00186
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.06163
A3 0.00000 0.16000
A4 0.09666 0.00000 0.16030
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00232 0.00290 0.16000 0.16983 0.21934
Eigenvalues --- 0.25000 0.55992 0.63002 1.61679
RFO step: Lambda=-2.17046510D-06.
Quartic linear search produced a step of -0.25146.
Iteration 1 RMS(Cart)= 0.01356612 RMS(Int)= 0.00011281
Iteration 2 RMS(Cart)= 0.00011814 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81571 -0.00019 -0.00005 -0.00013 -0.00018 1.81553
R2 1.81779 -0.00032 -0.00006 -0.00018 -0.00024 1.81755
R3 4.60083 -0.00007 0.00281 -0.02067 -0.01787 4.58297
R4 2.06243 -0.00105 0.00002 -0.00055 -0.00053 2.06189
A1 1.83545 0.00010 0.00002 0.00058 0.00060 1.83605
A2 3.01138 0.00013 0.01636 0.00114 0.01750 3.02888
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.22207 0.00012 -0.00985 -0.00034 -0.01019 3.21188
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.001047 0.000450 NO
RMS Force 0.000377 0.000300 NO
Maximum Displacement 0.021841 0.001800 NO
RMS Displacement 0.013613 0.001200 NO
Predicted change in Energy=-1.430629D-06

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
Reza 86



---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.019232 0.000000 -0.003774
2 1 0 -0.096431 0.000000 0.953855
3 1 0 0.926193 0.000000 -0.180521
4 7 0 3.272910 0.000000 -0.792504
5 7 0 4.291038 0.000000 -1.184844
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960736 0.000000
3 H 0.961804 1.527275 0.000000
4 N 3.385306 3.795027 2.425202 0.000000
5 N 4.469155 4.880975 3.511530 1.091107 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.006428 -2.317796 0.000000
2 1 0 0.920281 -2.614251 0.000000
3 1 0 0.052993 -1.357120 0.000000
4 7 0 0.000000 1.067503 0.000000
5 7 0 -0.146386 2.148746 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 594.0293711 2.8841297
2.8701944
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.6207469265 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A') (A") (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
Reza 87



(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A') (A") (A') (A") (A") (A') (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026845118 A.U. after 9 cycles
Convg = 0.9245D-09 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000174519 0.000000000 0.000028149
2 1 -0.000008229 0.000000000 -0.000117340
3 1 -0.000128893 0.000000000 0.000124898
4 7 0.000156816 0.000000000 -0.000151616
5 7 -0.000194213 0.000000000 0.000115908
-------------------------------------------------------------------
Cartesian Forces: Max 0.000194213 RMS 0.000108330


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000222878 RMS 0.000115785
Search for a local minimum.
Step number 11 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 2 3 4 5 6
7 8 9 10 11
Trust test= 1.37D+00 RLast= 2.70D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57959
R2 0.02462 0.59017
R3 -0.00130 -0.00028 0.00210
R4 0.02245 0.03966 -0.00227 1.62119
A1 0.01356 0.01409 0.00109 0.00060 0.16874
A2 0.00328 0.00514 0.00045 0.02265 -0.00233
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 0.00371 0.00695 0.00106 0.03767 -0.00350
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.05754
Reza 88



A3 0.00000 0.16000
A4 0.09141 0.00000 0.15418
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00202 0.00252 0.16000 0.16736 0.20824
Eigenvalues --- 0.25000 0.55965 0.60907 1.62463
RFO step: Lambda=-4.54840277D-07.
Quartic linear search produced a step of 0.20290.
Iteration 1 RMS(Cart)= 0.00476787 RMS(Int)= 0.00000500
Iteration 2 RMS(Cart)= 0.00000567 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81553 -0.00012 -0.00004 -0.00018 -0.00021 1.81531
R2 1.81755 -0.00018 -0.00005 -0.00026 -0.00030 1.81724
R3 4.58297 -0.00003 -0.00363 -0.00808 -0.01170 4.57126
R4 2.06189 -0.00022 -0.00011 -0.00006 -0.00017 2.06173
A1 1.83605 0.00003 0.00012 0.00020 0.00032 1.83637
A2 3.02888 0.00008 0.00355 -0.00661 -0.00306 3.02581
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.21188 0.00013 -0.00207 0.00491 0.00284 3.21472
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000223 0.000450 YES
RMS Force 0.000116 0.000300 YES
Maximum Displacement 0.007584 0.001800 NO
RMS Displacement 0.004771 0.001200 NO
Predicted change in Energy=-3.132696D-07

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.016146 0.000000 -0.005113
2 1 0 -0.096234 0.000000 0.952164
3 1 0 0.929595 0.000000 -0.179270
4 7 0 3.270238 0.000000 -0.790005
5 7 0 4.287024 0.000000 -1.185565
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960622 0.000000
3 H 0.961643 1.527242 0.000000
4 N 3.378813 3.790553 2.419009 0.000000
5 N 4.462145 4.876765 3.504990 1.091019 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Reza 89



Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.010179 -2.313707 0.000000
2 1 0 0.923566 -2.611228 0.000000
3 1 0 0.057587 -1.353233 0.000000
4 7 0 0.000000 1.065091 0.000000
5 7 0 -0.151798 2.145497 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 591.6064275 2.8935302
2.8794469
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.6588598746 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A') (A") (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A') (A") (A') (A") (A") (A') (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026845468 A.U. after 8 cycles
Convg = 0.3978D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 0.000002863 0.000000000 -0.000060439
2 1 -0.000002420 0.000000000 -0.000013688
3 1 0.000014626 0.000000000 0.000118725
4 7 -0.000058455 0.000000000 -0.000074419
5 7 0.000043385 0.000000000 0.000029821
Reza 90



-------------------------------------------------------------------
Cartesian Forces: Max 0.000118725 RMS 0.000044640


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000135200 RMS 0.000054991
Search for a local minimum.
Step number 12 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 3 4 5 6 7
8 9 10 11 12
Trust test= 1.12D+00 RLast= 1.24D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.57997
R2 0.02665 0.59589
R3 -0.00021 0.00178 0.00253
R4 0.03776 0.07192 0.00411 1.76365
A1 0.01386 0.01384 0.00069 -0.00817 0.16867
A2 0.02006 0.03254 0.00379 0.08069 -0.00944
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 0.03190 0.05260 0.00645 0.12995 -0.01517
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.05047
A3 0.00000 0.16000
A4 0.07706 0.00000 0.12598
A5 0.00000 0.00000 0.00000 0.25000
Eigenvalues --- 0.00207 0.00253 0.13804 0.16000 0.18064
Eigenvalues --- 0.25000 0.56008 0.61893 1.78488
RFO step: Lambda=-1.87558189D-07.
Quartic linear search produced a step of 0.76790.
Iteration 1 RMS(Cart)= 0.00403836 RMS(Int)= 0.00000176
Iteration 2 RMS(Cart)= 0.00000208 RMS(Int)= 0.00000000
Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81531 -0.00001 -0.00016 0.00004 -0.00012 1.81519
R2 1.81724 -0.00001 -0.00023 0.00009 -0.00015 1.81710
R3 4.57126 0.00000 -0.00899 -0.00202 -0.01101 4.56026
R4 2.06173 0.00003 -0.00013 0.00004 -0.00009 2.06164
A1 1.83637 0.00001 0.00024 0.00002 0.00027 1.83664
A2 3.02581 0.00009 -0.00235 0.00180 -0.00055 3.02527
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.21472 0.00014 0.00218 0.00003 0.00221 3.21693
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000135 0.000450 YES
RMS Force 0.000055 0.000300 YES
Maximum Displacement 0.006342 0.001800 NO
RMS Displacement 0.004039 0.001200 NO
Predicted change in Energy=-7.193366D-08

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Reza 91




Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.013460 0.000000 -0.006154
2 1 0 -0.095544 0.000000 0.950889
3 1 0 0.932521 0.000000 -0.178570
4 7 0 3.267293 0.000000 -0.788731
5 7 0 4.283668 0.000000 -1.185222
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960557 0.000000
3 H 0.961565 1.527284 0.000000
4 N 3.372798 3.786153 2.413184 0.000000
5 N 4.455952 4.872419 3.499076 1.090973 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.011274 -2.310054 0.000000
2 1 0 0.924158 -2.608906 0.000000
3 1 0 0.059846 -1.349716 0.000000
4 7 0 0.000000 1.062726 0.000000
5 7 0 -0.153457 2.142853 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 591.3318685 2.9020360
2.8878634
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 73 symmetry adapted basis functions of A' symmetry.
There are 28 symmetry adapted basis functions of A" symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
101 basis functions, 150 primitive gaussians, 107 cartesian
basis functions
12 alpha electrons 12 beta electrons
nuclear repulsion energy 52.6926550285 Hartrees.
NAtoms= 5 NActive= 5 NUniq= 5 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 101 RedAO= T NBF= 73 28
NBsUse= 101 1.00D-06 NBFU= 73 28
Initial guess read from the read-write file:
Initial guess orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Reza 92



Virtual (A') (A") (A') (A') (A') (A') (A") (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A') (A") (A') (A") (A") (A') (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -186.026845609 A.U. after 7 cycles
Convg = 0.8592D-08 -V/T = 2.0031
S**2 = 0.0000
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.000090071 0.000000000 -0.000116062
2 1 0.000006016 0.000000000 0.000042853
3 1 0.000077155 0.000000000 0.000124540
4 7 -0.000153517 0.000000000 -0.000036571
5 7 0.000160416 0.000000000 -0.000014760
-------------------------------------------------------------------
Cartesian Forces: Max 0.000160416 RMS 0.000079906


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Internal Forces: Max 0.000154839 RMS 0.000080376
Search for a local minimum.
Step number 13 out of a maximum of 20
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Update second derivatives using D2CorX and points 4 5 6 7 8
9 10 11 12 13
Trust test= 1.95D+00 RLast= 1.12D-02 DXMaxT set to 3.00D-01
The second derivative matrix:
R1 R2 R3 R4 A1
R1 0.60112
R2 0.06029 0.64940
R3 0.00537 0.01044 0.00360
R4 0.10077 0.17123 0.01833 1.93772
A1 0.00512 -0.00008 -0.00165 -0.03541 0.17238
A2 0.03176 0.04998 0.00669 0.09738 -0.01431
A3 0.00000 0.00000 0.00000 0.00000 0.00000
A4 0.05020 0.07986 0.01109 0.15511 -0.02274
A5 0.00000 0.00000 0.00000 0.00000 0.00000
A2 A3 A4 A5
A2 0.03517
A3 0.00000 0.16000
A4 0.05172 0.00000 0.08411
A5 0.00000 0.00000 0.00000 0.25000
Reza 93



Eigenvalues --- 0.00195 0.00259 0.07921 0.16000 0.17777
Eigenvalues --- 0.25000 0.56024 0.67116 1.99058
RFO step: Lambda=-2.50574917D-07.
Quartic linear search produced a step of 0.02283.
Iteration 1 RMS(Cart)= 0.00073272 RMS(Int)= 0.00000051
Iteration 2 RMS(Cart)= 0.00000059 RMS(Int)= 0.00000000
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
R1 1.81519 0.00004 0.00000 -0.00007 -0.00007 1.81512
R2 1.81710 0.00007 0.00000 -0.00011 -0.00011 1.81699
R3 4.56026 0.00002 -0.00025 0.00078 0.00053 4.56079
R4 2.06164 0.00015 0.00000 -0.00006 -0.00006 2.06158
A1 1.83664 -0.00002 0.00001 0.00013 0.00014 1.83677
A2 3.02527 0.00009 -0.00001 0.00168 0.00167 3.02694
A3 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
A4 3.21693 0.00014 0.00005 0.00077 0.00082 3.21775
A5 3.14159 0.00000 0.00000 0.00000 0.00000 3.14159
Item Value Threshold Converged?
Maximum Force 0.000155 0.000450 YES
RMS Force 0.000080 0.000300 YES
Maximum Displacement 0.001597 0.001800 YES
RMS Displacement 0.000733 0.001200 YES
Predicted change in Energy=-1.254035D-07
Optimization completed.
-- Stationary point found.
----------------------------
! Optimized Parameters !
! (Angstroms and Degrees) !
-------------------------- ----------------
----------
! Name Definition Value Derivative Info.
!
----------------------------------------------------------------------
----------
! R1 R(1,2) 0.9606 -DE/DX = 0.0
!
! R2 R(1,3) 0.9616 -DE/DX = 0.0001
!
! R3 R(3,4) 2.4132 -DE/DX = 0.0
!
! R4 R(4,5) 1.091 -DE/DX = 0.0002
!
! A1 A(2,1,3) 105.2316 -DE/DX = 0.0
!
! A2 L(3,4,5,-2,-1) 173.335 -DE/DX = 0.0001
!
! A3 L(3,4,5,-3,-2) 180.0 -DE/DX = 0.0
!
! A4 L(1,3,4,2,-1) 184.3165 -DE/DX = 0.0001
!
! A5 L(1,3,4,2,-2) 180.0 -DE/DX = 0.0
!
----------------------------------------------------------------------
----------

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Reza 94




Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -0.013460 0.000000 -0.006154
2 1 0 -0.095544 0.000000 0.950889
3 1 0 0.932521 0.000000 -0.178570
4 7 0 3.267293 0.000000 -0.788731
5 7 0 4.283668 0.000000 -1.185222
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960557 0.000000
3 H 0.961565 1.527284 0.000000
4 N 3.372798 3.786153 2.413184 0.000000
5 N 4.455952 4.872419 3.499076 1.090973 0.000000
Stoichiometry H2N2O
Framework group CS[SG(H2N2O)]
Deg. of freedom 7
Full point group CS NOp 2
Largest Abelian subgroup CS NOp 2
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.011274 -2.310054 0.000000
2 1 0 0.924158 -2.608906 0.000000
3 1 0 0.059846 -1.349716 0.000000
4 7 0 0.000000 1.062726 0.000000
5 7 0 -0.153457 2.142853 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 591.3318685 2.9020360
2.8878634

**********************************************************************

Population analysis using the SCF density.

**********************************************************************

Orbital symmetries:
Occupied (A') (A') (A') (A') (A') (A') (A') (A') (A") (A')
(A') (A")
Virtual (A') (A") (A') (A') (A') (A') (A") (A') (A') (A")
(A') (A') (A') (A") (A') (A') (A') (A') (A') (A')
(A') (A") (A') (A") (A') (A') (A") (A') (A") (A')
(A") (A') (A') (A') (A') (A') (A") (A") (A') (A')
(A") (A') (A') (A') (A') (A") (A') (A") (A") (A')
(A') (A') (A') (A') (A') (A') (A") (A') (A") (A")
(A') (A") (A') (A') (A') (A') (A') (A") (A') (A')
(A") (A') (A') (A") (A') (A") (A") (A') (A') (A')
(A') (A") (A") (A') (A') (A') (A') (A') (A')
Reza 95



The electronic state is 1-A'.
Alpha occ. eigenvalues -- -19.12657 -14.43698 -14.43511 -1.15522 -
1.01533
Alpha occ. eigenvalues -- -0.57785 -0.53549 -0.49123 -0.49118 -
0.45837
Alpha occ. eigenvalues -- -0.39212 -0.31737
Alpha virt. eigenvalues -- -0.04987 -0.04955 -0.01189 0.03469
0.06864
Alpha virt. eigenvalues -- 0.08039 0.08081 0.12037 0.12554
0.14376
Alpha virt. eigenvalues -- 0.15260 0.16036 0.19115 0.20558
0.23297
Alpha virt. eigenvalues -- 0.26546 0.29598 0.36869 0.51709
0.53574
Alpha virt. eigenvalues -- 0.58545 0.67268 0.68196 0.68523
0.69299
Alpha virt. eigenvalues -- 0.72228 0.74170 0.78990 0.79408
0.79430
Alpha virt. eigenvalues -- 0.79947 0.84950 0.88728 0.91446
0.97629
Alpha virt. eigenvalues -- 1.00177 1.02743 1.08290 1.09770
1.22176
Alpha virt. eigenvalues -- 1.22317 1.22361 1.30896 1.40177
1.54535
Alpha virt. eigenvalues -- 1.72826 1.73961 1.77264 1.80527
1.86004
Alpha virt. eigenvalues -- 1.90833 2.00552 2.21318 2.33939
2.56648
Alpha virt. eigenvalues -- 2.96886 3.63500 3.64001 3.72344
3.72867
Alpha virt. eigenvalues -- 3.75296 3.92113 3.92696 3.94799
3.96637
Alpha virt. eigenvalues -- 4.12526 4.31737 4.33044 4.37284
4.40018
Alpha virt. eigenvalues -- 4.57031 4.57050 4.70615 4.73660
4.73689
Alpha virt. eigenvalues -- 5.00525 5.22188 5.22335 5.57243
6.19110
Alpha virt. eigenvalues -- 6.22305 6.85340 6.87529 7.00330
7.27649
Alpha virt. eigenvalues -- 7.48657 35.09097 36.00191 49.89854
Condensed to atoms (all electrons):
1 2 3 4 5
1 O 7.955460 0.265472 0.285494 -0.002994 0.008700
2 H 0.265472 0.512877 -0.012133 -0.000939 0.001435
3 H 0.285494 -0.012133 0.408335 0.010861 0.018039
4 N -0.002994 -0.000939 0.010861 6.442898 0.669754
5 N 0.008700 0.001435 0.018039 0.669754 6.193052
Mulliken atomic charges:
1
1 O -0.512132
2 H 0.233289
3 H 0.289404
4 N -0.119581
5 N 0.109019
Sum of Mulliken charges= 0.00000
Atomic charges with hydrogens summed into heavy atoms:
Reza 96



1
1 O 0.010561
2 H 0.000000
3 H 0.000000
4 N -0.119581
5 N 0.109019
Sum of Mulliken charges= 0.00000
Electronic spatial extent (au): <R**2>= 371.2559
Charge= 0.0000 electrons
Dipole moment (field-independent basis, Debye):
X= 1.5736 Y= 1.3762 Z= 0.0000 Tot= 2.0905
Quadrupole moment (field-independent basis, Debye-Ang):
XX= -15.8185 YY= -21.6507 ZZ= -18.1104
XY= -4.2967 XZ= 0.0000 YZ= 0.0000
Traceless Quadrupole moment (field-independent basis, Debye-Ang):
XX= 2.7080 YY= -3.1242 ZZ= 0.4162
XY= -4.2967 XZ= 0.0000 YZ= 0.0000
Octapole moment (field-independent basis, Debye-Ang**2):
XXX= 2.2333 YYY= -1.5976 ZZZ= 0.0000 XYY= 13.1300
XXY= -4.6505 XXZ= 0.0000 XZZ= 0.2194 YZZ= 1.3069
YYZ= 0.0000 XYZ= 0.0000
Hexadecapole moment (field-independent basis, Debye-Ang**3):
XXXX= -16.6506 YYYY= -438.7757 ZZZZ= -16.6674 XXXY= 4.7769
XXXZ= 0.0000 YYYX= -22.2090 YYYZ= 0.0000 ZZZX= 0.0000
ZZZY= 0.0000 XXYY= -60.9919 XXZZ= -5.8484 YYZZ= -75.5722
XXYZ= 0.0000 YYXZ= 0.0000 ZZXY= 3.0021
N-N= 5.269265502847D+01 E-N=-5.426264367178D+02 KE=
1.854540289815D+02
Symmetry A' KE= 1.774671661185D+02
Symmetry A" KE= 7.986862863025D+00
Final structure in terms of initial Z-matrix:
O
H,1,B1
H,1,B2,2,A1
N,1,B3,2,A2,3,D1,0
N,2,B4,1,A3,4,D2,0
Variables:
B1=0.96055696
B2=0.96156531
B3=3.37279849
B4=4.87241935
A1=105.23160434
A2=108.31853574
A3=59.0954431
D1=0.
D2=0.
1|1|UNPC-UNK|FOpt|RB3LYP|6-311++G(2d,2p)|H2N2O1|PCUSER|02-Jul-2012|0||
# OPT RB3LYP/6-311++G(2D,2P) GEOM=CONNECTIVITY||Title Card Required||0
,1|O,-2.2462112177,0.,0.5394535861|H,-2.328295103,0.,1.496496902|H,-1.
3002299759,0.,0.3670374007|N,1.0345422529,0.,-0.243123149|N,2.05091700
72,0.,-0.6396144212||Version=IA32W-G03RevC.02|State=1-A'|HF=-186.02684
56|RMSD=8.592e-009|RMSF=7.991e-005|Dipole=0.6686975,0.,0.4788218|PG=CS
[SG(H2N2O1)]||@


WE'RE IN THE POSITION OF A VISITOR FROM ANOTHER
DIMENSION WHO COMES TO EARTH AND SEES A CHESS MATCH.
Reza 97



ASSUMING HE KNOWS IT'S A GAME, HE'S GOT TWO PROBLEMS:
FIRST, FIGURE OUT THE RULES, AND SECOND, FIGURE OUT HOW TO WIN.
NINETY PERCENT OF SCIENCE (INCLUDING VIRTUALLY ALL OF CHEMISRY)
IS IN THAT SECOND CATEGORY. THEY'RE TRYING TO APPLY
THE LAWS THAT ARE ALREADY KNOWN.

-- SHELDON GLASHOW, 1979
Job cpu time: 0 days 0 hours 4 minutes 13.0 seconds.
File lengths (MBytes): RWF= 20 Int= 0 D2E= 0 Chk=
8 Scr= 1
Normal termination of Gaussian 03 at Mon Jul 02 05:10:58 2012.















Reza 98



Appendix B
Gaussian Output file for Water-Carbon dioxide


Entering Link 1 = C:\G03W\l1.exe PID= 2456.

Copyright (c) 1988,1990,1992,1993,1995,1998,2003,2004, Gaussian, Inc.
All Rights Reserved.

This is the Gaussian(R) 03 program. It is based on the
the Gaussian(R) 98 system (copyright 1998, Gaussian, Inc.),
the Gaussian(R) 94 system (copyright 1995, Gaussian, Inc.),
the Gaussian 92(TM) system (copyright 1992, Gaussian, Inc.),
the Gaussian 90(TM) system (copyright 1990, Gaussian, Inc.),
the Gaussian 88(TM) system (copyright 1988, Gaussian, Inc.),
the Gaussian 86(TM) system (copyright 1986, Carnegie Mellon
University), and the Gaussian 82(TM) system (copyright 1983,
Carnegie Mellon University). Gaussian is a federally registered
trademark of Gaussian, Inc.

This software contains proprietary and confidential information,
including trade secrets, belonging to Gaussian, Inc.

This software is provided under written license and may be
used, copied, transmitted, or stored only in accord with that
written license.

The following legend is applicable only to US Government
contracts under FAR:

RESTRICTED RIGHTS LEGEND

Use, reproduction and disclosure by the US Government is
subject to restrictions as set forth in subparagraphs (a)
and (c) of the Commercial Computer Software - Restricted
Rights clause in FAR 52.227-19.

Gaussian, Inc.
340 Quinnipiac St., Bldg. 40, Wallingford CT 06492


---------------------------------------------------------------
Warning -- This program may not be used in any manner that
competes with the business of Gaussian, Inc. or will provide
assistance to any competitor of Gaussian, Inc. The licensee
of this program is prohibited from giving any competitor of
Gaussian, Inc. access to this program. By using this program,
the user acknowledges that Gaussian, Inc. is engaged in the
business of creating and licensing software in the field of
computational chemistry and represents and warrants to the
licensee that it is not a competitor of Gaussian, Inc. and that
it will not use this program in any manner prohibited above.
Reza 99



---------------------------------------------------------------


Cite this work as:
Gaussian 03, Revision C.02,
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven,
K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega,
G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota,
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala,
K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg,
V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain,
O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari,
J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford,
J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,
I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham,
C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill,
B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople,
Gaussian, Inc., Wallingford CT, 2004.

******************************************
Gaussian 03: IA32W-G03RevC.02 12-Jun-2004
31-Jul-2012
******************************************
%chk=en1.chk
%mem=6MW
%nproc=1
Will use up to 1 processors via shared memory.
-----------------------------------------------
# freq rb3lyp/6-311++g(2d,2p) geom=connectivity
-----------------------------------------------
1/10=4,30=1,38=1,57=2/1,3;
2/17=6,18=5,40=1/2;
3/5=4,6=6,7=1212,11=2,16=1,25=1,30=1,74=-5/1,2,3;
4/7=1/1;
5/5=2,38=5/2;
8/6=4,10=90,11=11/1;
11/6=1,8=1,9=11,15=111,16=1/1,2,10;
10/6=1/2;
6/7=2,8=2,9=2,10=2,18=1,28=1/1;
7/8=1,10=1,25=1/1,2,3,16;
1/10=4,30=1/3;
99//99;
-------------------
Title Card Required
-------------------
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
O
H 1 B1
H 1 B2 2 A1
C 1 B3 2 A2 3 D1 0
O 4 B4 1 A3 2 D2 0
Reza 100



O 4 B5 1 A4 5 D3 0
Variables:
B1 0.96078
B2 0.96086
B3 2.86451
B4 1.16011
B5 1.16055
A1 105.70885
A2 130.34805
A3 92.23431
A4 89.65638
D1 160.61877
D2 12.21601
D3 -179.95899



GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Initialization pass.
----------------------------
! Initial Parameters !
! (Angstroms and Degrees) !
---------------------- --------------------
--
! Name Value Derivative information (Atomic Units)
!
----------------------------------------------------------------------
--
! B1 0.9608 calculate D2E/DX2 analytically
!
! B2 0.9609 calculate D2E/DX2 analytically
!
! B3 2.8645 calculate D2E/DX2 analytically
!
! B4 1.1601 calculate D2E/DX2 analytically
!
! B5 1.1605 calculate D2E/DX2 analytically
!
! A1 105.7089 calculate D2E/DX2 analytically
!
! A2 130.3481 calculate D2E/DX2 analytically
!
! A3 92.2343 calculate D2E/DX2 analytically
!
! A4 89.6564 calculate D2E/DX2 analytically
!
! D1 160.6188 calculate D2E/DX2 analytically
!
! D2 12.216 calculate D2E/DX2 analytically
!
! D3 -179.959 calculate D2E/DX2 analytically
!
----------------------------------------------------------------------
--
Trust Radius=3.00D-01 FncErr=1.00D-07 GrdErr=1.00D-07
Reza 101



Number of steps in this run= 2 maximum allowed number of steps= 2.

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

Input orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 0.000000 0.000000 0.000000
2 1 0 0.000000 0.000000 0.960775
3 1 0 0.924969 0.000000 -0.260151
4 6 0 -2.059404 -0.724472 -1.854569
5 8 0 -2.865280 -0.747943 -1.020375
6 8 0 -1.280016 -0.711471 -2.714368
---------------------------------------------------------------------
Distance matrix (angstroms):
1 2 3 4 5
1 O 0.000000
2 H 0.960775 0.000000
3 H 0.960857 1.531740 0.000000
4 C 2.864512 3.562607 3.460276 0.000000
5 O 3.132158 3.562892 3.937429 1.160114 0.000000
6 O 3.084222 3.956174 3.375104 1.160547 2.320346
6
6 O 0.000000
Stoichiometry CH2O3
Framework group C1[X(CH2O3)]
Deg. of freedom 12
Full point group C1 NOp 1
Largest Abelian subgroup C1 NOp 1
Largest concise Abelian subgroup C1 NOp 1
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 8 0 -1.943427 -0.033803 -0.032263
2 1 0 -2.555934 -0.759150 0.115370
3 1 0 -2.454252 0.769138 0.100364
4 6 0 0.920534 0.011149 0.001460
5 8 0 0.983946 -1.147231 0.002038
6 8 0 0.895353 1.171423 0.002163
---------------------------------------------------------------------
Rotational constants (GHZ): 11.4251532 4.5454575
3.2533012
Standard basis: 6-311++G(2d,2p) (5D, 7F)
There are 128 symmetry adapted basis functions of A symmetry.
Integral buffers will be 262144 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
128 basis functions, 192 primitive gaussians, 136 cartesian
basis functions
16 alpha electrons 16 beta electrons
nuclear repulsion energy 104.5923821262 Hartrees.
Reza 102



NAtoms= 6 NActive= 6 NUniq= 6 SFac= 1.00D+00 NAtFMM= 60
Big=F
One-electron integrals computed using PRISM.
NBasis= 128 RedAO= T NBF= 128
NBsUse= 128 1.00D-06 NBFU= 128
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 3.60D-02 ExpMax= 8.59D+03 ExpMxC= 1.30D+03 IAcc=3 IRadAn=
5 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 5 IDoV=1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Initial guess orbital symmetries:
Occupied (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A)
Virtual (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A)
The electronic state of the initial guess is 1-A.
Requested convergence on RMS density matrix=1.00D-08 within 128
cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
SCF Done: E(RB+HF-LYP) = -265.115708970 A.U. after 10 cycles
Convg = 0.6803D-08 -V/T = 2.0031
S**2 = 0.0000
Range of M.O.s used for correlation: 1 128
NBasis= 128 NAE= 16 NBE= 16 NFC= 0 NFV= 0
NROrb= 128 NOA= 16 NOB= 16 NVA= 112 NVB= 112

**** Warning!!: The largest alpha MO coefficient is 0.16004292D+02

Symmetrizing basis deriv contribution to polar:
IMax=3 JMax=2 DiffMx= 0.00D+00
G2DrvN: will do 7 centers at a time, making 1 passes doing
MaxLOS=2.
FoFDir/FoFCou used for L=0 through L=2.
DoAtom=TTTTTT
Differentiating once with respect to electric field.
with respect to dipole field.
Differentiating once with respect to nuclear coordinates.
Integrals replicated using symmetry in FoFDir.
MinBra= 0 MaxBra= 2 Meth= 1.
IRaf= 0 NMat= 21 IRICut= 21 DoRegI=T DoRafI=T ISym2E= 2
JSym2E=2.
There are 21 degrees of freedom in the 1st order CPHF.
18 vectors were produced by pass 0.
AX will form 18 AO Fock derivatives at one time.
18 vectors were produced by pass 1.
18 vectors were produced by pass 2.
18 vectors were produced by pass 3.
Reza 103



18 vectors were produced by pass 4.
16 vectors were produced by pass 5.
7 vectors were produced by pass 6.
2 vectors were produced by pass 7.
Inv2: IOpt= 1 Iter= 1 AM= 1.80D-15 Conv= 1.00D-12.
Inverted reduced A of dimension 115 with in-core refinement.
Isotropic polarizability for W= 0.000000 24.55 Bohr**3.
End of Minotr Frequency-dependent properties file 721 does not
exist.

**********************************************************************

Population analysis using the SCF density.

**********************************************************************

Orbital symmetries:
Occupied (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A)
Virtual (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A)
(A) (A) (A) (A)
The electronic state is 1-A.
Alpha occ. eigenvalues -- -19.19439 -19.19433 -19.14316 -10.34971 -
1.15570
Alpha occ. eigenvalues -- -1.11632 -1.03173 -0.55752 -0.55309 -
0.51603
Alpha occ. eigenvalues -- -0.50992 -0.50937 -0.40912 -0.36632 -
0.36548
Alpha occ. eigenvalues -- -0.33395
Alpha virt. eigenvalues -- -0.02813 0.00981 0.02688 0.03767
0.04107
Alpha virt. eigenvalues -- 0.06403 0.06770 0.08280 0.13415
0.14873
Alpha virt. eigenvalues -- 0.15913 0.16500 0.17982 0.19642
0.20647
Alpha virt. eigenvalues -- 0.21163 0.24362 0.25646 0.26677
0.28245
Alpha virt. eigenvalues -- 0.28589 0.32156 0.35228 0.51703
0.53366
Alpha virt. eigenvalues -- 0.54431 0.55185 0.59191 0.59993
0.65137
Alpha virt. eigenvalues -- 0.67573 0.71184 0.74043 0.82211
0.85529
Alpha virt. eigenvalues -- 0.89629 0.94209 0.95009 0.96149
0.97290
Alpha virt. eigenvalues -- 0.98634 1.01587 1.05137 1.09973
1.11731
Alpha virt. eigenvalues -- 1.13439 1.14829 1.27397 1.35216
1.36916
Reza 104



Alpha virt. eigenvalues -- 1.41818 1.43600 1.45745 1.66903
1.69154
Alpha virt. eigenvalues -- 1.75570 1.76754 1.88049 1.89277
1.91081
Alpha virt. eigenvalues -- 1.94515 2.04302 2.20472 2.26465
2.37242
Alpha virt. eigenvalues -- 2.40351 2.46054 2.55426 2.66227
2.74788
Alpha virt. eigenvalues -- 2.78582 2.85660 3.14400 3.22646
3.37294
Alpha virt. eigenvalues -- 3.37359 3.40382 3.70892 3.74053
3.77606
Alpha virt. eigenvalues -- 3.89299 4.00780 4.07259 4.20128
4.95294
Alpha virt. eigenvalues -- 4.99289 5.00149 5.04369 5.06861
5.56077
Alpha virt. eigenvalues -- 5.76925 5.94651 6.16356 6.64049
6.65570
Alpha virt. eigenvalues -- 6.75037 6.75628 6.83758 6.85864
6.91409
Alpha virt. eigenvalues -- 6.92051 6.99892 7.17309 7.24645
7.25193
Alpha virt. eigenvalues -- 7.25979 7.42153 7.45139 24.23667
49.87078
Alpha virt. eigenvalues -- 49.95083 49.95998
Condensed to atoms (all electrons):
1 2 3 4 5 6
1 O 7.949071 0.278167 0.278991 -0.005248 -0.005460 -
0.002166
2 H 0.278167 0.486689 -0.015646 0.000458 0.000533 -
0.000042
3 H 0.278991 -0.015646 0.486745 0.000459 0.000064
0.000898
4 C -0.005248 0.000458 0.000459 4.625655 0.466189
0.461541
5 O -0.005460 0.000533 0.000064 0.466189 7.919013 -
0.155434
6 O -0.002166 -0.000042 0.000898 0.461541 -0.155434
7.926220
Mulliken atomic charges:
1
1 O -0.493354
2 H 0.249841
3 H 0.248490
4 C 0.450947
5 O -0.224905
6 O -0.231017
Sum of Mulliken charges= 0.00000
Atomic charges with hydrogens summed into heavy atoms:
1
1 O 0.004976
2 H 0.000000
3 H 0.000000
4 C 0.450947
5 O -0.224905
6 O -0.231017
Sum of Mulliken charges= 0.00000
Reza 105



APT atomic charges:
1
1 O -0.516521
2 H 0.261173
3 H 0.262120
4 C 1.187541
5 O -0.595233
6 O -0.599081
Sum of APT charges= 0.00000
APT Atomic charges with hydrogens summed into heavy atoms:
1
1 O 0.006773
2 H 0.000000
3 H 0.000000
4 C 1.187541
5 O -0.595233
6 O -0.599081
Sum of APT charges= 0.00000
Electronic spatial extent (au): <R**2>= 347.5029
Charge= 0.0000 electrons
Dipole moment (field-independent basis, Debye):
X= -2.2014 Y= 0.1050 Z= 0.4558 Tot= 2.2506
Quadrupole moment (field-independent basis, Debye-Ang):
XX= -13.8334 YY= -23.9233 ZZ= -22.6678
XY= 0.0705 XZ= -1.2801 YZ= -0.0258
Traceless Quadrupole moment (field-independent basis, Debye-Ang):
XX= 6.3081 YY= -3.7818 ZZ= -2.5263
XY= 0.0705 XZ= -1.2801 YZ= -0.0258
Octapole moment (field-independent basis, Debye-Ang**2):
XXX= -28.1823 YYY= -0.1518 ZZZ= 0.2087 XYY= -10.7099
XXY= -0.0223 XXZ= 3.3596 XZZ= 1.4980 YZZ= 0.0318
YYZ= 0.2859 XYZ= 0.0809
Hexadecapole moment (field-independent basis, Debye-Ang**3):
XXXX= -188.1772 YYYY= -110.9033 ZZZZ= -19.8759 XXXY= 2.6028
XXXZ= -9.0381 YYYX= -0.0898 YYYZ= -0.0195 ZZZX= -0.6727
ZZZY= -0.0160 XXYY= -51.6080 XXZZ= -51.0935 YYZZ= -21.8497
XXYZ= -0.2541 YYXZ= -0.8724 ZZXY= -0.0422
N-N= 1.045923821262D+02 E-N=-8.345501909694D+02 KE=
2.642850605033D+02
Exact polarizability: 21.503 -0.455 33.432 -0.018 -0.019 18.708
Approx polarizability: 25.223 -1.131 58.108 -0.272 -0.018 23.449
Full mass-weighted force constant matrix:
Low frequencies --- -4.5410 -0.0007 -0.0005 0.0012 5.7402
7.4606
Low frequencies --- 39.1162 53.2356 92.7809
Diagonal vibrational polarizability:
186.6728726 483.7959940 2413.4188106
Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman
scattering
activities (A**4/AMU), depolarization ratios for plane and unpolarized
incident light, reduced masses (AMU), force constants (mDyne/A),
and normal coordinates:
1 2 3
A A A
Frequencies -- 38.9175 53.1228
92.7790
Reza 106



Red. masses -- 1.9359 1.2595
7.2181
Frc consts -- 0.0017 0.0021
0.0366
IR Inten -- 54.0291 216.9319
0.4885
Atom AN X Y Z X Y Z X Y
Z
1 8 -0.02 0.06 -0.05 0.01 0.02 0.10 0.53 0.00
0.01
2 1 -0.35 0.43 0.43 -0.30 0.12 -0.73 0.49 0.03
-0.02
3 1 0.53 0.37 0.16 -0.03 0.10 -0.58 0.57 0.04
-0.04
4 6 0.00 -0.04 0.00 0.00 -0.01 0.00 -0.23 0.00
0.00
5 8 0.16 -0.03 0.00 0.05 -0.01 -0.01 -0.22 0.00
0.00
6 8 -0.16 -0.04 0.01 -0.05 -0.01 -0.01 -0.21 0.00
0.00
4 5 6
A A A
Frequencies -- 132.7092 178.4179
663.6544
Red. masses -- 1.1514 1.5540
12.8966
Frc consts -- 0.0119 0.0291
3.3466
IR Inten -- 15.7500 24.9010
46.8722
Atom AN X Y Z X Y Z X Y
Z
1 8 0.00 -0.06 0.01 0.01 0.13 0.00 0.01 0.00
0.00
2 1 -0.10 0.14 0.58 0.55 -0.28 0.28 0.01 0.00
0.01
3 1 0.07 0.12 -0.78 -0.60 -0.20 -0.32 -0.01 -0.01
0.01
4 6 0.00 0.01 0.00 0.00 -0.03 0.00 0.88 0.03
0.00
5 8 -0.04 0.01 -0.03 0.09 -0.03 -0.01 -0.33 -0.03
0.00
6 8 0.04 0.02 0.03 -0.09 -0.04 0.01 -0.34 0.00
0.00
7 8 9
A A A
Frequencies -- 678.5520 1364.2517
1636.8052
Red. masses -- 12.8594 15.9903
1.0850
Frc consts -- 3.4885 17.5346
1.7127
IR Inten -- 29.2841 0.2081
76.2890
Atom AN X Y Z X Y Z X Y
Z
Reza 107



1 8 0.00 0.00 -0.01 0.00 0.00 0.00 -0.07 0.00
0.02
2 1 0.00 0.00 0.01 -0.01 0.01 0.00 0.52 -0.46
-0.13
3 1 0.00 0.00 0.02 -0.01 0.00 0.00 0.58 0.38
-0.14
4 6 0.00 0.00 0.88 0.03 0.00 0.00 0.00 0.00
0.00
5 8 0.00 0.00 -0.33 -0.04 0.71 0.00 0.00 0.00
0.00
6 8 0.00 0.00 -0.33 0.02 -0.71 0.00 0.00 0.00
0.00
10 11 12
A A A
Frequencies -- 2400.7740 3822.5388
3925.7697
Red. masses -- 12.8595 1.0441
1.0829
Frc consts -- 43.6695 8.9890
9.8334
IR Inten -- 656.1705 10.7278
72.3248
Atom AN X Y Z X Y Z X Y
Z
1 8 0.00 0.00 0.00 -0.05 0.00 0.01 0.00 -0.07
0.00
2 1 -0.02 0.01 0.00 0.42 0.56 -0.10 0.45 0.53
-0.11
3 1 0.02 0.01 0.00 0.34 -0.62 -0.09 -0.37 0.59
0.10
4 6 -0.03 0.88 0.00 0.00 0.00 0.00 0.00 0.00
0.00
5 8 0.02 -0.33 0.00 0.00 0.00 0.00 0.00 0.00
0.00
6 8 0.01 -0.33 0.00 0.00 0.00 0.00 0.00 0.00
0.00

-------------------
- Thermochemistry -
-------------------
Temperature 298.150 Kelvin. Pressure 1.00000 Atm.
Atom 1 has atomic number 8 and mass 15.99491
Atom 2 has atomic number 1 and mass 1.00783
Atom 3 has atomic number 1 and mass 1.00783
Atom 4 has atomic number 6 and mass 12.00000
Atom 5 has atomic number 8 and mass 15.99491
Atom 6 has atomic number 8 and mass 15.99491
Molecular mass: 62.00039 amu.
Principal axes and moments of inertia in atomic units:
1 2 3
EIGENVALUES -- 157.96210 397.04281 554.74150
X 0.99999 0.00077 -0.00498
Y -0.00077 1.00000 -0.00024
Z 0.00498 0.00024 0.99999
This molecule is an asymmetric top.
Rotational symmetry number 1.
Rotational temperatures (Kelvin) 0.54832 0.21815 0.15613
Reza 108



Rotational constants (GHZ): 11.42515 4.54546 3.25330
Zero-point vibrational energy 89649.9 (Joules/Mol)
21.42684 (Kcal/Mol)
Warning -- explicit consideration of 5 degrees of freedom as
vibrations may cause significant error
Vibrational temperatures: 55.99 76.43 133.49 190.94
256.70
(Kelvin) 954.85 976.28 1962.85 2354.99
3454.17
5499.77 5648.30

Zero-point correction= 0.034146
(Hartree/Particle)
Thermal correction to Energy= 0.040944
Thermal correction to Enthalpy= 0.041888
Thermal correction to Gibbs Free Energy= 0.002488
Sum of electronic and zero-point Energies= -265.081563
Sum of electronic and thermal Energies= -265.074765
Sum of electronic and thermal Enthalpies= -265.073821
Sum of electronic and thermal Free Energies= -265.113221

E (Thermal) CV S
KCal/Mol Cal/Mol-Kelvin Cal/Mol-Kelvin
Total 25.693 17.602 82.925
Electronic 0.000 0.000 0.000
Translational 0.889 2.981 38.293
Rotational 0.889 2.981 25.057
Vibrational 23.915 11.641 19.575
Vibration 1 0.594 1.981 5.313
Vibration 2 0.596 1.976 4.698
Vibration 3 0.602 1.954 3.601
Vibration 4 0.613 1.921 2.906
Vibration 5 0.629 1.869 2.345
Q Log10(Q) Ln(Q)
Total Bot 0.717341D-01 -1.144274 -2.634789
Total V=0 0.364493D+15 14.561689 33.529529
Vib (Bot) 0.559876D-13 -13.251908 -30.513646
Vib (Bot) 1 0.531691D+01 0.725659 1.670892
Vib (Bot) 2 0.389021D+01 0.589973 1.358462
Vib (Bot) 3 0.221499D+01 0.345371 0.795246
Vib (Bot) 4 0.153513D+01 0.186145 0.428614
Vib (Bot) 5 0.112634D+01 0.051671 0.118977
Vib (V=0) 0.284483D+03 2.454056 5.650672
Vib (V=0) 1 0.584037D+01 0.766440 1.764794
Vib (V=0) 2 0.442221D+01 0.645639 1.486639
Vib (V=0) 3 0.277072D+01 0.442592 1.019107
Vib (V=0) 4 0.211450D+01 0.325208 0.748820
Vib (V=0) 5 0.173234D+01 0.238632 0.549471
Electronic 0.100000D+01 0.000000 0.000000
Translational 0.191888D+08 7.283047 16.769835
Rotational 0.667708D+05 4.824587 11.109022
***** Axes restored to original set *****
-------------------------------------------------------------------
Center Atomic Forces (Hartrees/Bohr)
Number Number X Y Z
-------------------------------------------------------------------
1 8 -0.000042598 0.000000431 -0.000081803
Reza 109



2 1 -0.000001782 -0.000013224 0.000041199
3 1 0.000052030 0.000014191 0.000036957
4 6 0.000017845 -0.000000690 -0.000001905
5 8 0.000012347 0.000003917 -0.000006825
6 8 -0.000037842 -0.000004624 0.000012377
-------------------------------------------------------------------
Cartesian Forces: Max 0.000081803 RMS 0.000030550
----------------------------------------------------------------------
--
Internal Coordinate Forces (Hartree/Bohr or radian)
Cent Atom N1 Length/X N2 Alpha/Y N3 Beta/Z
J
----------------------------------------------------------------------
--
1 O
2 H 1 0.000041( 1)
3 H 1 0.000040( 2) 2 -0.000090( 6)
4 C 1 0.000003( 3) 2 -0.000096( 7) 3 0.000016( 10)
0
5 O 4 -0.000014( 4) 1 -0.000011( 8) 2 0.000003( 11)
0
6 O 4 -0.000035( 5) 1 0.000044( 9) 5 -0.000002( 12)
0
----------------------------------------------------------------------
--
Internal Forces: Max 0.000095664 RMS 0.000045033


GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d
Berny optimization.
Search for a local minimum.
Step number 1 out of a maximum of 2
All quantities printed in internal units (Hartrees-Bohrs-Radians)
Second derivative matrix not updated -- analytic derivatives used.
The second derivative matrix:
B1 B2 B3 B4 B5
B1 0.53953
B2 -0.00487 0.53933
B3 0.00033 0.00034 0.00422
B4 0.00018 -0.00037 -0.00008 1.03818
B5 -0.00041 0.00018 0.00033 0.08928 1.03545
A1 0.02999 0.02906 0.00098 0.00324 -0.00387
A2 0.00069 -0.00075 -0.00007 0.00628 -0.00614
A3 -0.00050 0.00015 0.00566 -0.00927 -0.00242
A4 0.00032 -0.00064 0.00625 -0.00262 -0.00934
D1 0.00003 0.00021 0.00009 -0.00069 0.00084
D2 0.00005 -0.00003 -0.00001 0.00046 -0.00045
D3 0.00012 0.00008 -0.00005 0.00019 -0.00026
A1 A2 A3 A4 D1
A1 0.16026
A2 0.00186 0.00439
A3 -0.00410 -0.00464 0.19105
A4 0.00184 0.00558 0.17146 0.19306
D1 -0.00058 -0.00098 0.00107 -0.00066 0.00172
D2 0.00016 -0.00049 0.00005 -0.00007 0.00225
D3 -0.00006 -0.00014 0.00008 0.00003 0.00173
Reza 110



D2 D3
D2 0.00340
D3 0.00201 0.18181
Eigenvalues --- 0.00009 0.00148 0.00402 0.00499 0.02321
Eigenvalues --- 0.15577 0.18185 0.36354 0.53917 0.54431
Eigenvalues --- 0.94770 1.12629
Angle between quadratic step and forces= 49.61 degrees.
Linear search not attempted -- first point.
Variable Old X -DE/DX Delta X Delta X Delta X New X
(Linear) (Quad) (Total)
B1 1.81560 0.00004 0.00000 0.00016 0.00016 1.81576
B2 1.81576 0.00004 0.00000 0.00004 0.00004 1.81579
B3 5.41314 0.00000 0.00000 -0.00317 -0.00317 5.40998
B4 2.19230 -0.00001 0.00000 0.00029 0.00029 2.19259
B5 2.19312 -0.00003 0.00000 -0.00032 -0.00032 2.19279
A1 1.84497 -0.00009 0.00000 -0.00045 -0.00045 1.84452
A2 2.27500 -0.00010 0.00000 -0.06083 -0.06083 2.21417
A3 1.60979 -0.00001 0.00000 -0.01685 -0.01685 1.59295
A4 1.56480 0.00004 0.00000 0.01709 0.01709 1.58188
D1 2.80333 0.00002 0.00000 0.01395 0.01395 2.81728
D2 0.21321 0.00000 0.00000 -0.01654 -0.01654 0.19667
D3 -3.14088 0.00000 0.00000 0.00000 0.00000 -3.14088
Item Value Threshold Converged?
Maximum Force 0.000096 0.000450 YES
RMS Force 0.000045 0.000300 YES
Maximum Displacement 0.060830 0.001800 NO
RMS Displacement 0.019905 0.001200 NO
Predicted change in Energy=-3.485368D-06

GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGra
d

1|1|UNPC-UNK|Freq|RB3LYP|6-311++G(2d,2p)|C1H2O3|PCUSER|31-Jul-2012|1||
# FREQ RB3LYP/6-311++G(2D,2P) GEOM=CONNECTIVITY||Title Card Required||
0,1|O|H,1,B1|H,1,B2,2,A1|C,1,B3,2,A2,3,D1,0|O,4,B4,1,A3,2,D2,0|O,4,B5,
1,A4,5,D3,0||B1=0.960775|B2=0.96085709|B3=2.86451227|B4=1.16011449|B5=
1.16054743|A1=105.70885225|A2=130.34805142|A3=92.23431135|A4=89.656384
52|D1=160.61877297|D2=12.21601263|D3=-179.95899355||Version=IA32W-G03R
evC.02|State=1-A|HF=-265.115709|RMSD=6.803e-009|RMSF=3.055e-005|Dipole
=0.694156,0.0355653,0.5485371|DipoleDeriv=-0.4294866,-0.0076121,0.0145
238,-0.0198998,-0.666111,-0.0187802,0.0063417,-0.0094766,-0.453964,0.2
559271,-0.0051547,-0.0422114,-0.0024038,0.3425949,0.0068029,-0.051128,
-0.0015929,0.1849972,0.1717131,-0.0015891,-0.0243533,0.0080357,0.34091
22,-0.0023963,-0.0054283,-0.0026879,0.2737361,1.4776914,0.0514963,-0.8
677425,0.050437,0.5028307,0.0053113,-0.8722508,0.004671,1.5821014,-0.7
642891,-0.0234477,0.4655623,-0.0243973,-0.2596891,0.0113597,0.4597998,
0.0096754,-0.7617222,-0.7115558,-0.0136928,0.4542212,-0.0117718,-0.260
5379,-0.0022974,0.4626655,-0.0005891,-0.8251485|Polar=26.9717294,0.631
3977,18.8649727,-6.0415601,0.2520757,27.8061691|PG=C01 [X(C1H2O3)]|NIm
ag=0||0.54150064,0.00136435,0.00050041,-0.11542643,0.00102788,0.607348
31,-0.04639235,-0.00047550,-0.03426451,0.04848323,-0.00040629,-0.00003
469,0.00012561,0.00024530,0.00035960,0.02540132,-0.00002686,-0.5245287
2,-0.01618869,0.00006413,0.53953485,-0.49169571,-0.00023028,0.15044452
,-0.00286284,0.00003328,-0.00915570,0.49502915,-0.00003483,-0.00017886
,-0.00034644,0.00004808,-0.00033829,0.00001701,0.00021043,0.00051558,0
.09095980,-0.00037965,-0.07921357,0.05061824,0.00005285,-0.01458272,-0
.14154140,0.00014042,0.09288793,-0.00477502,0.00035494,0.00588431,0.00
Reza 111



344868,0.00076394,0.00027165,-0.00162622,-0.00081987,-0.00210315,0.967
89589,-0.00027111,-0.00152299,0.00010815,0.00054856,0.00022940,0.00002
175,0.00004011,0.00031841,0.00032777,0.01757858,0.15263441,0.00469279,
0.00031195,-0.00621273,-0.00182735,-0.00067479,-0.00092783,0.00136847,
0.00084309,0.00396727,-0.87871078,-0.02142546,1.08382076,-0.00036460,-
0.00041600,-0.00179023,-0.00105716,-0.00015861,0.00003824,0.00035454,0
.00005470,0.00045921,-0.49369756,-0.01136248,0.43786510,0.51742558,-0.
00070127,0.00059792,0.00006814,-0.00002758,-0.00027244,0.00001978,-0.0
0012808,0.00003097,-0.00025158,-0.01097469,-0.07590163,0.01238332,0.01
353040,0.03825565,-0.00385298,-0.00051853,0.00270129,0.00131431,0.0004
3067,0.00029013,-0.00082861,-0.00048136,-0.00181516,0.43937453,0.01283
233,-0.53033381,-0.49865995,-0.01341405,0.56002302,0.00172704,-0.00059
750,-0.00484766,-0.00161957,-0.00047762,-0.00036682,0.00080109,0.00054
149,0.00160729,-0.47124577,-0.00653366,0.43661176,-0.02266079,-0.00169
878,0.06265270,0.49299799,0.00004916,0.00063821,-0.00098334,-0.0003388
6,0.00005642,-0.00009580,0.00007454,-0.00034782,0.00011019,-0.00690290
,-0.07575760,0.00856189,-0.00164801,0.03728953,0.00115093,0.00876607,0
.03812125,-0.00177450,-0.00041478,-0.00009458,0.00034798,0.00000153,0.
00021428,-0.00028728,-0.00017273,-0.00124375,0.43528345,0.00813545,-0.
55031366,0.06208762,0.00119440,-0.03086547,-0.49565728,-0.00874387,0.5
8230318||0.00004260,-0.00000043,0.00008180,0.00000178,0.00001322,-0.00
004120,-0.00005203,-0.00001419,-0.00003696,-0.00001785,0.00000069,0.00
000190,-0.00001235,-0.00000392,0.00000683,0.00003784,0.00000462,-0.000
01238|||@


IT IS THE GODS' CUSTOM TO BRING LOW ALL THINGS OF SURPASSING
GREATNESS.
-- HERODOTUS
IT IS THE LOFTY PINE THAT BY THE STORM IS OFTENER TOSSED;
TOWERS FALL WITH HEAVIER CRASH WHICH HIGHER SOAR.
-- HORACE
THE BIGGER THEY COME, THE HARDER THEY FALL.
-- BOB FITZSIMONS HEAVYWEIGHT CHAMPION, 1897-1899
Job cpu time: 0 days 0 hours 15 minutes 29.0 seconds.
File lengths (MBytes): RWF= 20 Int= 0 D2E= 0 Chk=
17 Scr= 1
Normal termination of Gaussian 03 at Tue Jul 31 14:02:29 2012.








QUANTUM CHEMICAL STUDY ON ATMOSPHERICALLY IMPORTANT WATER COMPLEXES: A GAUSSIAN APPROACH

A Thesis Presented to The Faculty of the College of Graduate Studies Lamar University

In Partial Fulfillment of the Requirements for the Degree Master of Engineering Science by Shakib Bin Reza July 2012

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