This lecture covers the theoretical and conceptual foundations of quantum dynamics in molecular systems. Particular attention is taken to derive and compare quantum and classical approximations which can be used to simulate the dynamics of molecular systems and the reaction rate constant used in chemical kinetics.
Learning objective
The theory of quantum dynamics is derived from the time-dependent Schrödinger equation. This is illustrated with molecular examples including tunnelling, recurrences, nonadiabatic crossings. We consider thermal distributions, correlation functions, interaction with light and nonadiabatic effects. Quantum scattering theory is introduced and applied to discuss molecular collisions. The dynamics of systems with a very large number of quantum states are discussed to understand the transition from microscopic to macroscopic dynamics. A rigorous rate theory is obtained both from a quantum-mechanical picture as well as within the classical approximation. The approximations leading to conventional transition-state theory for polyatomic reactions are discussed. In this way, relaxation and irreversibility will be explained which are at the foundation of statistical mechanics.
By the end of the course, the student will have learned many ways to simplify the complex problem posed by quantum dynamics. They will understand when and why certain approximations are valid in different situations and will use this to make quantitative and qualitative predictions about how different molecular systems behave.
Lecture notes
Will be available online.
Literature
D. J. Tannor, Introduction to Quantum Mechanics: A Time-Dependent Perspective R. D. Levine, Molecular Reaction Dynamics S. Mukamel, Principles of Nonlinear Optical Spectroscopy
Prerequisites / Notice
529-0422-00L Physical Chemistry II: Chemical Reaction Dynamics
Performance assessment
Performance assessment information (valid until the course unit is held again)
Performance assessment as a semester course