Chemical kinetics – the study of the rates of chemical reactions – is a very practical subject, used widely in many branches of science and engineering. Chemical reaction dynamics provides the link between macroscopic rate constants and elementary state-to-state transitions caused by atomic and molecular interactions. This course will study chemical reaction rates from both a top-down approach, looking at bulk reaction mechanisms, and from a bottom-up approach, starting from the Schrodinger equation and scattering theory.
This course is intended for both chemists and physicists, with a physical chemistry “flavor.” The contents and level of the course will be tailored according to the background and expectations of students enrolled in the course.
The first part of the course deals with chemical rate equations. We will begin by exploring the relation between rate constants and microscopic cross sections. Next we will solve the rate equations for various types of reactions using both analytic and numerical methods. Attention will be given to condensed phase reactions, including catalysis, reactions on surfaces, and oscillating reactions. In the second part of the course we will study various methods of calculating rate constants. We will develop the concept of potential energy surfaces and apply it to the transition state theory of bimolecular reactions. We will also use the statistical RRKM theory to calculate unimolecular rate constants. In the last part of the course we will apply classical, semi-classical, and quantum mechanical methods to chemical reaction dynamics. Topics we will study include elastic scattering, energy transfer, non-radiative transitions, and coherent control of chemical reactions. The emphasis on various topics will depend on the interests of the class.
Part I. Kinetics
- Overview
- The link between macroscopic and microscopic views of kinetics
- Microscopic reversibility and detailed balancing
- Mechanisms and Rate Laws
- First and second order reactions
- Relaxation methods for fast reactions
- Consecutive and branched reactions
- Numerical solutions
- Condensed Phase Reactions
1. Solution reactions
2. Catalysis
3. Oscillating reactions
4. Surface reactions
D. Bimolecular Reactions
1. Collision theory
2. Transition state theory
E. Unimolecular kinetics
1. Lindeman mechanism
2. RRKM theory
Part II. Dynamics
A. Center of mass transformation; Newton diagrams
B. Elastic scattering
1. Classical treatment
2. Quantum mechanical treatment
C. Inelastic scattering
D. Reactive scattering
1. Potential energy surfaces
2. Topics in reaction dynamics
3. Non-adiabatic reactions
4. Resonances
E. Photo-induced processes
1. Multiphoton excitation
2. Coherent control