BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE,

Pilani
Pilani Campus
AUGS/AGSR Division

SECOND SEMESTER 2022-2023

Course Handout (Part II)

Date: 10.01.2024

In addition to Part I (General Handout for all courses appended to the time table) this portion gives further specific details regarding this course.
Course No. : CHEM F244
Course Title : Physical Chemistry III
Instructor-in-charge : PRASHANT UDAY MANOHAR
Scope and objective of the course: This course is designed in continuation to the Physical chemistry courses I and II, already offered to the
students. Physical Chemistry III course is composed of two parts. In the first portion, students would be exposed to the molecular symmetry,
principles of group theory, and its application in molecular spectroscopy. The second portion provides a comprehensive survey of various
approximation methods in quantum chemistry.
Course Description: Symmetry - symmetry operations, point groups, reducible and irreducible representations, character tables, SALC,
degeneracy, vibrational modes IR-Raman activity identification; stationary state perturbation theory; virial and Hellmann-Feynmann theorems;
polyatomic molecules: SCF MO treatment, basis sets, population analysis, molecular electrostatic potentials, configuration interaction, Moller
Plesset perturbation theory; Density Functional Theory: Hohenberg-Kohn theorems, Kohn-Sham self consistent field approach, exchange
correlation functional; molecular mechanics.
Text Book (TB): TB-1: “Chemical Applications of Group Theory”, F. Albert Cotton, Wiley Student Edition, Third Edition. TB-2: “Quantum
Chemistry”, Ira N. Levine, PHI Learning Private Limited, Sixth Edition, 2012.
Reference Books (RB): “Quantum Chemistry”, Donald A McQuarrie, University Science Books (First Indian Edition 2003, Viva Books Private
Limited)

Course Plan:

Lecture Lecture Session Reference to Text Learning Outcome

No.

Module 1: Molecular Symmetry and symmetry group

1 Definitions and Properties of a group, examples of groups, TB-1 2.1- 2.4 The symmetry elements and the
Theorems of Group subgroups, classes corresponding mathematical
Theory operators will be learned. The
2-3 Symmetry elements Plane, center of inversion, proper axis, and TB-1 3.1 – 3.9 recipe of determining symmetry
and operations improper axis, product of symmetry group of given molecule will be
operations, point groups learned. The effect of symmetry
4 Application of Dipole moments, optical activity TB-1 3.10 group on optical properties of
symmetry operations molecules will be understood.
5-6 Group Theory Symmetry Point Group, Symmetry TB-1 3.11 – 3.14
classification of molecules
Module 2: Representation of Groups
Equivalent and Unitary representation, reducible TB-1 4.2 – 4.5 Mathematical aspects of
7-8 reducible representation, transformation operators. symmetry groups will be
representation learned in more details. The
Irreducible The “Great Orthogonality Theorem”, TB-1 4.2 – 4.5 great orthogonality theorem
9-11
Class notes will be introduced along with
representation characters, criterion for irreducibility, character
its applications in quantum
tables and their construction chemistry and molecular
12-13 Representation and Invariance of Hamiltonian operator under TB-1 5.1 – 5.3 spectroscopy.
quantum mechanics transformation, direct product representation,
vanishing integrals
14-15 Symmetry adapted Projection operators, construction of SALCs TB-1 6.1 – 6.3
linear combination using projection operators.
(SALC)

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE,
Pilani
Pilani Campus
AUGS/AGSR Division

16-19 Molecular vibrations Normal coordinates, vibrational levels, IR TB-1 10.1 – 10.8
spectra, Raman spectra, selection rules.
Module 3: Electronic structure of polyatomic molecules: (a) Theorems
20-23 Theorems of Virial theorem and Chemical Bonding, TB-2 14.1 – 14.7 Concepts of kinetic energy,
molecular quantum Hellmann-Feynman theorem, Electrostatic potential energy and its
mechanics theorem components will be revisited
in the light of the theorems in
molecular quantum mechanics.
Module 4: Electronic structure of polyatomic molecules: (b) Molecular Orbital treatment
SELF Approximation The Hartree SCF Method and Hartree-Fock RB 1 Basics of Hartree-Fock Theory
STUDY Theorem of Many SCF Method for many electron atoms to be recapitulated
Electron Atoms
24 - 29 Molecular SCF-MO treatment, basis functions, population TB-2 13.15, 15.1 – Computational aspects of
electronic structure analysis, molecular electrostatic potential, 15.5, 15.6 – 15.9 Hartree-Fock will be learned
calculations localized MOs, SCF-MO treatment of H2O in detail. The basis sets and
their
features will be introduced.
30 - 32 Configuration Configuration state functions, occupied and TB-2 11.3, 16.1, Concepts of size-consistency
Interaction virtual molecular orbitals, excitation energy class notes and size-extensivity will be
calculation. understood
33 - 34 Stationary state Perturbation treatment of non-degenerate and TB-2 9.1 – 9.7 Degenerate perturbation theory
perturbation theory degenerate states. will be learned. Application of
35 - 37 Møller– Plesset Many body perturbation theory, electron TB-2 16.2 non-degenerate perturbation to
Perturbation theory correlation effects, Møller– Plesset Hartree-Fock wavefunction
perturbation of 2nd, 3rd, and 4th order will be learned.
Module 5: Electronic structure of polyatomic molecules: (c) Alternate approaches
SELF Valence-Bond Coupling of electrons, bond eigenfunction, TB-2 16.8
STUDY approach application of Valence-Bond treatment to
different polyatomic molecules
38 - 42 Density Functional Hohenberg-Kohn Theorem, Kohn-Sham TB-2 16.4, class Basic concepts of DFT will be
Theory method, exchange correlation functional, notes understood.
hybrid functional
Tutorial hour: The tutorial hour will be utilized for review of the topics covered in the lectures, problem solving and for conducting a part
of the continuous evaluation.

Continuous Evaluation: Continuous Evaluation will include quizzes conducted during the contact hours (including extra classes scheduled
for the same, if any), take-home assignment(s), etc.

Attendance policy: It is strongly recommended that students attend the classes for more effective teaching-learning experience.
Evaluation Scheme:
Component Duration Weightage Date & Time
Continuous Evaluation (partly open-book) May vary for quizzes and 30% Throughout the semester
assignments (60 marks)
Mid-semester Examination (Closed-book) 90 minutes 30% (60 marks) As per the time table
Comprehensive Examination (partly Open- 180 minutes 40% (80 marks) As per the time table
book)

Consultation Hour: To be announced in the class

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE,
Pilani
Pilani Campus
AUGS/AGSR Division

E-mail of the instructor: [email protected]

Notice: Notices concerning this course will be displayed on nalanda-aws.bits-pilani.ac.in and/or on the Department of Chemistry Notice
Board. For brief announcements, other forums such as Whatsapp group may also be used.

Make-up Policy: Refer to Part-I of the handout for details. Make-ups may not be granted to the students with attendance lower than 90%.

Instructor in charge

CHEM F244

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