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NORTH LAKHIMPUR COLLEGE (AUTONOMOUS)

A Project Report On-

THEORETICAL STUDIES OF FEW
MOLECULES
Submitted to:-
Department of Chemistry
For Partial Fulfilment of the requirement of Certificate Course in-

“Analytical & Computational Chemistry”

Submitted By:-
ANKUR BISWAKARMA
B.Sc. 6Th Semester
Roll No: 15BS160
 NORTH LAKHIMPUR COLLEGE (AUTONOMOUS)
DEPARTMENT OF CHEMISTRY

Dr. Raghab Parajuli

M.Sc. (Ph.D.)
Assistant Professor
Assam

CERTIFICATE

This is to certify that the Project Report entitled “THEORETICAL STUDIES OF

FEW MOLECULES” submitted by “ANKUR BISWAKARMA, 6th Semester,
Department of Chemistry”, North Lakhimpur College (Autonomous) has been
completed under my supervision at the Department of Chemistry, North Lakhimpur
College (Autonomous) for partial fulfillment of the Bachelor of Science in Chemistry
under Dibrugarh University.

(Mr. Diganta Kalita) (Dr. Raghab Parajuli)

Head Supervisor

Department of Chemistry

North Lakhimpur College (Autonomous)

Date:
 ACKNOWLEDGEMENT

I would like to warmly acknowledge and express my deep sense of gratitude and
indebtedness to the supervisor of the project work Dr. Raghab Parajuli Sir, who helped us a
lot and guided properly to complete this dissertation.
I would like to thank the faculty members of Department of Chemistry, North
Lakhimpur College (Autonomous) for allowing me to complete this project work in the
computer laboratory and for their cooperation.

Date:……/……../………… DEPARTMENT OF CHEMISTRY

NORTH LAKHIMPUR COLLEGE (AUTONOMOUS)
CONTENTS:

1. Introduction
1.1. Introduction to Computational Chemistry
1.2. The necessity of Computational Chemistry
1.3. Different Methods of Theoretical Calculations
1.4. Basis Set:
1.5. History
2. Present Work
2.1. Study of BF3
2.2. Study of C2H2
2.3. Study of c2H4
2.4. Study of C6H6
2.5 Study of CH3 Free Radical
2.6. Study of CH3-
2.7. Study of CH3+
2.8. Study of CH4
2.9. Study of H2O
2.10. Study of NH3
3. Discussions
4. Conclusion
5. References

Theoretical studies of few important molecules using Ab-initio Hartree Fock

(HF) and Density function Theory (DFT) methods.

1. INTRODUCTION:
1.1. INTRODUCTION TO COMPUTATIONAL CHEMISTRY:
 Chemistry is the science dealing with construction, transformation, and properties of
molecules. The term theoretical chemistry may be defined as the mathematical description of
chemistry where mathematical methods are combined with fundamental laws of physics to
study processes of chemical relevance.
Currently, there are two ways to approach theoretical chemistry problems.
Computational theoretical chemistry and non-computational theoretical chemistry.
The term computational chemistry is usually used when a mathematical method is
sufficiently well developed that it can be automated for implementation on a computer.
Computational chemistry is the application of chemical, mathematical and computing skills
to the solution of interesting chemical problems. It uses computers to generate information
such as properties of molecules or simulated experimental results. Very few aspects of
chemistry can be computed exactly, but almost every aspect of chemistry has been described
in a qualitative or approximate quantitative computational scheme. The biggest mistake that
computational chemists can make is to assume that any computed number is exact. However,
just as not all spectra are perfectly resolved, often a qualitative are approximate computation
can give useful insight into chemistry if we understand what it tells us and what it doesn’t.
Computational chemistry has become a useful way to investigate material that is too
difficult to find or too expensive to purchase. It also helps chemists to make predictions
before running the actual experiments so that they can be better prepared for making
observations.

1.2. THE NECESSITY OF COMPUTATIONAL CHEMISTRY:

Computational chemistry has become very useful to investigate for those materials
which are too expensive to buy or difficult to obtain. It helps chemists to predict before
running the actual experiments so that they can be better prepared for making observations.
Using the chemistry software following particulars can be performed –
• Electronic structure determinations,
• Geometry optimizations,
• Frequency calculations,
• Definition of transition structures and reaction paths,
• Protein calculations, i.e. docking,
• Electron and charge distributions calculations,
• Calculations of potential energy surfaces (PES),
• Calculations of rate constants for chemical reactions (kinetics)
• Thermodynamic calculations- the heat of reactions, the energy of activation, etc.
• Calculation of many other molecular and balk physical and chemical properties.
1.3. DIFFERENT METHODS OF THEORETICAL CALCULATIONS:
The most important numerical techniques are Ab-initio, semi-empirical and molecular
mechanics.

a) Ab initio Method:
The term “Ab initio” is a Latin word which means “From the beginning“. This name
is given to computations which are derived directly from theoretical principles, with no
inclusions of experimental data.
The most common and simplest type of Ab initio electronic structure calculations is
calle3d Hartree Fock scheme, an extension of molecular orbital theory in which the correlated
electron-electron repulsion is not especially taken into account, only its average effect is
included in the calculations.
The energy calculated are usually in units called Hartree (1H=27.2114 eV) and
approximate energies calculated are all equal and greater than the exact energy.

b) Density Functional Theory (DFT) Method:

According to DFT, the electronic energy (E) is expressed as a function of
electron density and is denoted as E[p]. As against a function in which a basic variable is a
number, for example, f(x) = sin x is a function of x, in the functional, the basic variable is a
function and there is a one to one correspondence between the variable and the functional:
The expectation value of energy
Λ
E[ Ψ ]=(∫ Ψ∗H Ψdτ )/(∫ Ψ∗Ψdτ )

The advantage with the DFT method is that the central quantity of interest in it is
electron density which is a 3D quantity, in place of wave function which is 3N dimensional,
N being the number of electrons.

c) Semi-Empirical and Empirical Method:

Semi-empirical calculations are set up with the same general structures as HF
calculations. Within this framework, certain pieces of information, such as two-electron
integrals are approximately or completely omitted.
In order to correct for the errors introduced by omitting part of the calculation, the
parameterized, by curve fitting in a few parameters or numbers, in order to give best possible
agreement with experimental data.
The good side of semi-empirical calculations is that they are much faster than the Ab-
initio calculations. The bad side of semi-empirical calculations is that the results can be erratic.
If the molecule under study is similar to molecules in the database used to parameterize the
method, then the results may be very good. If this molecule is significantly different from
anything in the parameterization set, the answers may be poor. Semi-empirical calculations
have been very successful in computational organic chemistry, where there are only a few
elements used extensively and the molecules are of moderate size. However, semi-empirical
methods have been devised specifically for the description of inorganic chemistry as well.
Molecular mechanic approach: If a molecule is too big to effectively use a semi-empirical
treatment, it is still possible to model its behavior by avoiding quantum mechanics. This is
done by constructing a simple expression for “molecular force field”, i.e. the potential energy
as a function of all atomic positions, and using it study molecular properties without the need
to compute a wave function or total electron density. The energy expression consists of simple
classical
Equations, such as the harmonic oscillator equation in order to describe the energy
associated with bond stretching, bending, rotation and intermolecular forces, such as Van

1.4. BASIS SET:

A basis set in theoretical and computational chemistry is a set of functions (called basis
functions) that is used to represent the electronic wave function in the Hartree–Fock method
or density-functional theory in order to turn the partial differential equations of the model into
algebraic equations suitable for efficient implementation on a computer. In principle, a
complete (infinite) basis set should be used for high accuracy. But in practice, the finite basis
set is used.
Several types of atomic orbitals can be used: Gaussian-type orbitals, Slater-type orbitals, or
numerical atomic orbitals. Out of the three, Gaussian-type orbitals are by far the most often
used, as they allow efficient implementations of Post-Hartree–Fock methods.

1. Slater Type Orbitals (STO) basis set

2. Gaussian Basis set
1. STO:
Atomic orbital to be used for high accuracy in calculations should be a linear
combination of several Slater Type Functions. However, at the minimum, one may
choose a set of STOs, one for each occupied orbital. Such a basis set is called
“Minimal Basis Set”. For example, in H2O molecule, the minimal basis set consists of
five STOs for 1s, 2s, 2px, 2py, 2pz of oxygen and two 1s STOs for two hydrogen
atoms.
2. GAUSSIAN BASIS:
Boys (1950) proposed the use of Gaussian type function in place of STO. A
Gaussian function at a point centered around atom A is defined as
p q r
X G =N x yz
A A
−ar 2
A eA

Where N is normalized constant; x, y, z are Cartesian coordinates of the point (p, q, r)

are small positive integers including zero, ‘a’ is a variable parameter, ‘r’ is the radial
distance of the point from the nucleus A.
* Pople basis sets:
The notation for the split-valence basis sets arising from the group of John Pople is typically
X-YZg. In this case, X represents the number of primitive Gaussians comprising each core
atomic orbital basis function. The Y and Z indicate that the valence orbitals are composed of
two basis functions each, the first one composed of a linear combination of Y primitive
Gaussian functions, the other composed of a linear combination of Z primitive Gaussian
functions. In this case, the presence of two numbers after the hyphens implies that this basis
set is a split-valence double-zeta basis set. Split-valence triple- and quadruple-zeta basis sets
are also used, denoted as X-YZWg, X-YZWVg, etc. Here is a list of commonly used split-
valence basis sets of this type:
3-21G
3-21G* - Polarization functions on heavy atoms
3-21G** - Polarization functions on heavy atoms and hydrogen
3-21+G - Diffuse functions on heavy atoms
3-21++G - Diffuse functions on heavy atoms and hydrogen
3-21+G* - Polarization and diffuse functions on heavy atoms
3-21+G** - Polarization functions on heavy atoms and hydrogen, as well as diffuse
functions on heavy atoms
4-21G
4-31G
6-21G
6-31G
6-31G*
6-31+G*
6-311G
6-311G*
The 6-31G* basis set (defined for the atoms H through Zn) is a valence double-zeta polarized
basis set that adds to the 6-31G set six d-type Cartesian-Gaussian polarization functions on
each of the atoms Li through Ca and ten f-type Cartesian Gaussian polarization functions on
each of the atoms Sc through Zn.

Pople basis sets are somewhat outdated, as correlation-consistent or polarization-consistent

basis sets typically yield better results with similar resources. Also note that some Pople basis
sets have grave deficiencies that may lead to incorrect results.

1.5 HISTORY:
 Building on the founding discoveries in the history of quantum mechanics, the first
theoretical calculation in the chemistry were those of Walter Heitler and Fritz London in
1927.
With the development of computer technology in 1940, the solution of the elaborate
wave equation for complex atomic system began to the realizable objective.
In the early 1950s, the first empirical atomic orbital calculations were carried out.
The first Ab initio Hartree Fock calculations on diatomic molecules were carried out in 1556s
at MIT using a basis set of Slater orbitals. For diatomic molecules, a systematic study using a
minimum basis set and first calculation with a larger basis set were published by Rancil and
Nesbet respectively in 1950.
In the early 1970s, efficient Ab initio computer programs such as ATMOL,
Gaussian, IBMOL, and POLYAYTOM, began to be used to speed up Ab initio calculation of
molecular orbitals. Of these four programs, only Gaussian is now widely expanded.
The journal of computational chemistry was first published in 1980.

DISCUSSIONS:

By observing the above data (those obtained from computational methods) and comparing
with the values that provided by Literature, the following conclusions can be drawn-

1. DFT always gives the lowest energy for all the molecules. So we may conclude that structure of
molecule obtained from DFT is more stable than those obtained from other methods.

2. It is found that in case of most of the molecules (studied for this Project Work), values of bond
length obtained from all four methods are close to the standard one. In case of C2H4, all the
methods give quite good results for the C=C bond. However, DFT gives the closest value to the
standard value. It is also found that in case of C 2H2, H2O molecules, DFT gives highest accurate
values of bond lengths than other methods.
 But in case of NH3, it is not same i.e. DFT does not give the most appropriate value of bond
length, but HF method using 6-31G** basis set calculate the closest value to standard one.

3. In case of C6H6, CH3 [Free Radical], C2H4, C2H2, CH4 molecules, the dipole moment is found
0.0000 Debye which is consistent with Literature Value.

In case of H2O, the values of dipole moment that obtained from the four methods HF/6-31G**, HF/6-
31G, HF/STO-3G, B3LYP/6-31G** are 2.1481 Debye, 2.5005 Debye, 1.7092 Debye, 2.0424 Debye
respectively. And literature provides that the dipole moment of H 2O is 1.8546 Debye; so in case of HF
method using STO-3G basis set, the value of dipole moment is closest to the standard one.

In case of NH3, HF method using 6-31G basis set gives the closest value to the standard one.
It may indicate that in case of polar molecules HF method using suitable basis sets give more
accurate value.
3. CONCLUSION:
From the study of the given molecules following conclusions can be drawn –
 The structure of a molecule from 631-G** is the most stable.
 The bond angles of a molecule in the three basic sets are almost equal, but
those in case of 631-G** and 631-G are more close to each other. Similar in
the case of bond length too.
 Dipole moment values are equal in all the three basic sets.

4. REFERENCES:
 Computational Chemistry- Wikipedia
 Introduction to Computational Chemistry- CCL.net
 Computational Chemistry using PC, 3rd Edition, Donald W. Rogers, Published by
John Wiley & Sons, Inc., 2003.
 Essentials of Computational Chemistry: Theories and Models, 2nd edition
Christopher J Cramer, Published by John Wiley & Sons, Inc., 2004.
 Introduction to Computational Chemistry, Second Edition, Frank Jensen,
Published by John Wiley & Sons, Inc., 2007.
 Theory and Applications in Computational Chemistry: The First Decade of the
Second Millennium, Pavia, Italy.
Published by: American Institute of Physics, 2012.
 Quantum Chemistry, (5th Edition), Ira N Levine, Published by Prentice Hall
(1999).
 Fundamentals of Computational Chemistry: A Guide for Organic Chemists, Hui-
Wen Shih, MacMillan Group Meeting, June 17, 2009.

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