Chemical kinetics and transition state theory

This course will cover calculating rate constants using two basic models: collision theory and transition state theory (TST). TST will particularly be discussed in detail with solving multiple examples and discussion of limitations and extensions. The course assumes knowledge of basic statistical mechanics, particularly Boltzmann distribution and partition functions. These concepts will be briefly revised, but not derived in detail. Knowledge of basic rate theory will be helpful, although will be covered in the course.
INTENDED AUDIENCE :NonePREREQUISITES : Introduction to chemical kinetics and dynamics.
Either Module 6 of https://nptel.ac.in/courses/122/101/122101001/ Or https://nptel.ac.in/courses/104/106/104106089/INDUSTRIES SUPPORT :None

COURSE LAYOUT

Week 1:Lecture 1: Rate: the reaction velocity Lecture 2: Its elementary - rate law equations Lecture 3: Arrhenius equation: what's the fuss about? Lecture 4: Dance of atoms: from Newton to Hamilton Lecture 5: Boltzmann distribution: a story of Hamilton, Liouville and Boltzmann Lecture 6: Maxwell Boltzmann distribution: how fast are molecules moving?Week 2:Lecture 7: Kinetic theory of collisions: initial estimate Lecture 8: Boltzmann distribution and kinetic theory of collisions Lecture 9: Kinetic theory of collisions: a discussion Lecture 10: Kinetic theory of collisions: reactive cross section Lecture 11: Problem solving session 1 Lecture 12: Problem solving session 2Week 3: Lecture 13: Kinetic theory of collision and equilibrium constant Lecture 14: Critique of kinetic theory of collisions Lecture 15: Transition state theory and partition functions Lecture 16: Partitioning the partition function Lecture 17: Translating, rotating and vibrating quantum mechanically Lecture 18: Partition function and equilibrium constant Lecture 19: What is a transition state?Week 4:Lecture 20: A puzzle: cars on highway Lecture 21: Transition state theory: derivation 1 Lecture 22: Practical calculation of TST rate Lecture 23: Calculating TST rate for the reaction H+HBr Lecture 24: Collision theory as a special case of TST Lecture 25: TST: an intuitive proof in one dimensionWeek 5:Lecture 26: Rate as a flux across a dividing surface Lecture 27: Transition state theory: derivation 2 from dynamical perspective Lecture 28: Discussion of the assumptions of TST Lecture 29: Thermodynamic formulation of TST Lecture 30: Problem solving session 3 Lecture 31: Problem solving session 4Week 6:Lecture 32: Hills and valleys of potential energy surfaces Lecture 33: Molecular dynamics: rolling spheres on potential energy surfaces Lecture 34: Predictions from potential energy surfaces - rotational vs vibrational energies Lecture 35: Free energy and potential of mean force Lecture 36: Transmission coefficient and molecualr dynamics Lecture 37: Problem solving session 5Week 7:Lecture 38: Microcanonical rate constant: putting balls in jars Lecture 39: Microcanonical rate constant: RRK model Lecture 40: Microcanonical rate constant: magic of Marcus - RRKM model Lecture 41: Canonical TST from micrononical RRKM model Lecture 42: Sum and density of statesWeek 8:Lecture 43: Unimolecular decay - revisited Lecture 44: Unimolecular decay: RRK's approach Lecture 45: Unimolecular decay: RRKM

Teaching Assistants

Amitava Giri

I am a PhD student at Department of Chemistry, IIT Bombay. I also completedmy MSc from IITBombay. During my PhD tenure I worked as a Teaching Assistant in various courses(Introductory Quantum Chemistry, Computers in Chemistry, Molecular Energetics and Dynamics)at Chemistry Department.

Harsimran KaurPost Doctoral fellow, IIT BombayEducation: Msc. Chemistry, University of Delhi, 2011-2013, Ph.D.: University of Delhi, 2014-2019
I am a post-doctoral fellow in the Department of Chemistry, IIT Bombay. I did my BSc(H) and MSc. In Chemistry from University of Delhi. I completed my PhD. From the Department of Chemistry, University of Delhi. My PhD research was focused on the development of a theoretical formalism to deal with coulomb interactions in exciton complexes of 2-D and 3-D anisotropic quantum dots. As a post-doc fellow at IITB with Prof. Amber Jain’s group, I am working in the field of quantum-classical dynamics.
I can be reached at [email protected]