DFT STUDY ON DIHYDROGEN BOND

INTERACTIONS BY SUBSTITUTION IN
XH3Si.NCH and
NCH.HM(X=H,F,Cl,Br;M=Li,Na,BeH,MgH)
COMPLEXES
Dissertation submitted to Nallamuthu Gounder Mahalingam
college In partial fulfillment of the requirements for the award
of the degree of
MASTER OF SCIENCE IN PHYSICS

Submitted by
K.PUNITHA VALLI (15-PP-17)

Under the guidance of

Dr.M.KARTHIKA, M.Sc., M.Phil., PGDCA., Ph.D.

POST GRADUATE & RESEARCH

DEPARTMENT OF PHYSICS

NALLAMUTHU GOUNDER MAHALINGAM COLLEGE

(AUTONOMOUS, AFFILIATED TO BHARATHIAR UNIVERSITY,

COIMBATORE)

(Re-Accredited with A Grade by NAAC)

(An ISO 9001:2008 Certified Institution)

Pollachi-642 001
MARCH 2017

CERTIFICATE
 CERTIFICATE
This is to certify that the project report entitled DFT STUDY ON DIHYDROGEN
BOND INTERACTIONS BY SUBSTITUTION IN XH 3Si.NCH and NCH.HM
(X=H,F,Cl,Br;M=Li,Na,BeH,MgH) COMPLEXES submitted to Nallamuthu Gounder
Mahalingam college (Autonomous) affiliated to Bharathiar University in partial fulfillment of
the requirements for the award of the degree of Master of Science in Physics is a record of
original work done by K.PUNITHAVALLI (15-PP-17 ) during the period 2015-2017 of her
study in the Department of Physics, Nallamuthu Gounder Mahalingam College
(Autonomous), Pollachi, under the guidance and the dissertation has not formed the basis for
the award of any Degree/Diploma/Associateship/Fellowship or other similar title to any
candidate of any University.

Countersigned

Project Guide Head of the Department

Submitted for the viva-voce examination held on..at Nallamuthu Gounder

Mahalingam College, Pollachi.

Place:

Date: Examiners

1.

2.
 DECLARATIO
N
DECLARATION
I, K.PUNITHAVALLI (15-PP-17) hereby declare that the dissertation entitled DFT
STUDY ON DIHYDROGEN BOND INTERACTIONS BY SUBSTITUTION IN
XH3Si.NCH and NCH.HM (X=H,F,Cl,Br;M=Li,Na,BeH,MgH) COMPLEXES
submitted to Nallamuthu Gounder Mahalingam College(Autonomous) affiliated to Bharathiar
University, in partial fulfillment of the requirements for the award of the Degree of Master of
Science in Physics is a record of original research work done by me during the period 2015-
2017 of my study under the supervision and guidance of Dr.M.KARTHIKA,
M.Sc.,M.Phil.,PGDCA.,Ph.D. Assistant Professor, Department of Physics, Nallamuthu
Gounder Mahalingam College(Autonomous), Pollachi and the project has not formed the
basis for the award of any Degree/ Associateship / Fellowship or other similar title to any
candidate of any University.

Place: Signature of the Candidate

Date:

(K.PUNITHAVALLI)
 ACKNOWLEDGEMENT
ACKNOWLEDGEMENT
I take immense pleasure in expressing my deep sense of gratitude to my guide
Dr.M.KARTHIKA, Assistant Professor, Department of Physics, Nallamuthu Gounder
Mahalingam College, Pollachi, for her valuable guidance, suggestions and constant
encouragement throughout my course of study.

I express my deep sense of gratitude and respect to Dr.R.KANAKARAJU, Associate

Professor and Head of the Department of Physics, Nallamuthu Gounder Mahalingam College
(Autonomous), Pollachi, for his timely help and encouragement.

I put forth my greatest acknowledgement and gratitude to Dr.P.M.PALANISAMY,

Principal, Nallamuthu Gounder Mahalingam College (Autonomous),Pollachi, for his
unconditional support.

I express my respect towards all the faculty members of the Department of Physics,
Nallamuthu Gounder Mahalingam College (Autonomous), Pollachi, for their lovable care and
motivation throughout my study.

I convey my regards to S.KAVITHA, Ph.D. Scholar, Department of Physics,

Nallamuthu Gounder Mahalingam College (Autonomous), Pollachi, for their valuable
information and timely support throughout my project work.

I have a great pleasure in expressing my deep sense of gratitude to my family

members and my friends for their keen attention, affection, co-operation and for their
gracious blessings.

Above all, I thank Almighty for giving me an excellent opportunity to work with a
crew of good people and for protecting and guiding us all throughout my life.

K.PUNITHAVALLI
 PREFACE
PREFACE

Classical mechanics does not correctly describe the behaviour of very small particles
such as the electron and nuclei of atoms and molecules. The behaviour of such particles is
described by a set of laws called quantum mechanics. Quantum mechanics is the science of
the very small: the body of scientific principles that explains the behaviour of matter and its
interactions with energy on the scale of atoms and subatomic particles.

Quantum mechanics is a branch of Physics which deals with physical phenomena at

nanoscopic scale. Owing to the several limitations we were in a need of new theory which led
to the birth of quantum mechanics. In 1925 Erwin Schrodinger, Werner Heisenberg, Max
Born, Paul Dirac and so many others were pioneers in the field of developing quantum
mechanics. This theory can be applied to nuclei, atoms molecules and matter. The theory
brought forth several new predictions, all could be experimentally verified. In quantum
mechanics, probabilistic measurements are made because of uncertainty principles. Quantum
chemistry applies quantum mechanics to interpret molecular spectra thereby allowing
experimental determination of molecular properties such as bond length, bond angle, and
dipole moment. With the development of fast digital computers, approximate solutions for
more complicated molecules became possible and are one of the main aspects of
computational chemistry.

Noncovalent interaction is of great importance in chemistry and biochemistry. They

are responsible for the formation, stability and biological activity of many macromolecules in
living systems. The hydrogen bond (HB) probably the most widely studied and analyzed
class of noncovalent interactions. In, recent years, much attention has been paid to a specific
intermolecular interaction involving tetra, pnicogen, chalcogen and halogen atoms. A tetral
bond refers to the noncovalent interaction (NCI) between a group-IV atom (C,Si,Ge or Sn) in
a molecule with a lewis base centre on other. The formation of tetral bonding can be
explained by a region of positive electrostatic potential which is present on the outermost
portion of some covalently bonded group IV atom surface, opposite to the covalent bond.
This electron-deficient region is referred as a -hole.

The dihydrogenbond is a special kind of HB, arising from the close approach of a
protonic H atom and a hydridic H atom. This interaction is typically characterized by
unusually short H.H internuclear separation that is less than or equal to the sum of the
Vander Waals radii of the two hydrogen atoms, and a normally linear R-H.H bond angle.

The present study examines the density functional theory (DFT) study on dihydrogen
bond interactions by substitution in XH3Si.NCH and NCH.HM(X=H,F,Cl,Br and
M=Li,Na,BeH,MgH) at B3LYP/aug-cc-pVTZ level of theory. The interplay of these
interactions has not yet been determined theoretically or experimentally.

Chapter 1- outlines the origin of quantum mechanics, properties of molecules and

computational details along with the details of present work.

Chapter 2- gives a detailed introduction to various quantum mechanical methods that have
been used to study the molecular systems.

Chapter 3-gives a detailed description of basis set used in molecular computational analysis.

Chapter 4-contains the results and discussion of the present work.

 CONTENTS
CONTENTS

TITLE PAGE NO

CHAPTER-I

1.1. Noncovalent interaction 1

1.2. Cooperative effects 1

1.3. Properties of molecules 2

1.3.1. Sodium hydride 2

1.3.2. Magnesium hydride 2

1.3.3. Beryllium hydride 2

1.3.4. Silicon hydride 3

1.3.5. Lithium hydride 3

1.4. Present work 4

1.5. Computational details 4

CHAPTER-II

2.1. Quantum chemical methods 5

2.1.1. Molecular mechanics 5

2.1.2. Electronics structure method 6

2.2. Semi-empirical method 6

2.3. AB initio method 7

 2.3.1. The Fock methods 8

2.3.2. Hartree-Fock self consistent field theory 10

2.4. Moller-Plesset perturbation theory 11

2.4.1. Rayleigh-Schrdinger perturbation theory (RS-PT) 11

2.4.2. Moller-Plesset-perturbation original formulation 12

2.4.3. Use of Moller- Plesset perturbation methods 13

2.5. Density functional theory (DFT) methods 13

2.5.1. Derivation and formulation 14

CHAPTER-III

3.1. Basis set 17

3.2. Minimal basis set 18

3.3. Split-valance basis set 18

3.4. Pople basis sets 19

3.5. Correlation consistent basis set 20

3.6. Other split valence basis set 21

3.7. Plane wave basis set 21

3.7. Real space basis set 22

CHAPTER-IV

Results and discussion

4.1. Geometry 24

4.2. Geometrical Parameters 24

4.2.1. Bond length 24

4.2.2. Bond angle 24

4.3. Energetical parameters

 4.3.1. Total energy 25

4.3.2. Dipole moment 25

4.3.3. Mulliken atomic charge 26

Tables 27

Figures 31

Graphs 34

Conclusion 35

Reference 36
CHAPTER I
CHAPTER II
CHAPTER III
CHAPTERIV
FIGURES
TABLES
GRAPHS
CONCLUSION
REFERENCE