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Chemistry 508: Chemical Kinetics and Reaction Dynamics

Course Level: 
Graduate Level
Academic Year: 
2014/2015

Textbook: 
Paul L. Houston, Chemical Kinetics and Reaction Dynamics, Dover Publications. (Recommended)
William L. Hase, Joseph Francisco, Jeffrey I. Steinfeld, Chemical Reaction Dynamics, Prentice Hall.
Raphael D. Levine, Molecular Reaction Dynamics, Cambridge University Press.
Tomas Baer, William L. Hase, Unimolecular Reaction Dynamics: Theory and Experiments, Oxford University Press.
Course Outline:

1) Review of macroscopic kinetics: reaction order, molecularity, the Arrhenius equation.

2) Potential energy functions and surfaces: intermolecular energy, origin of intermolecular forces, potential energy surfaces, reaction coordinate.

3) Microscopic kinetics: the total and differential reaction cross sections, the relationship between the rate constant and the reaction cross-section, the relationship between the threshold energy and the activation energy.

4) Collision Theory: simple collision theory.

5) Review of statistical mechanics: partition functions, ideal monatomic gas, ideal diatomic gas, equilibrium constants.

6) Transition state theory: assumptions, statistical mechanics formulation of transition state theory, thermodynamic formulation of transition state theory, structure of the transition state and the A factor, applications of transition state theory, isotope effects, tunneling.

7) Reaction dynamics: collisions of real molecules, the Lennard-Jones potential, elementary scattering theory.

8) Experimental reaction dynamics: bulb methods, reagent specification, product distributions, molecular beams, reagent specification, product detection.

9) Reaction dynamics and potential energy surfaces: potential energy surfaces, calculations of kinetic properties from potential energy surfaces, dynamics calculations vs transition state theory.

10) Unimolecular reactions: The Lindemann theory, the Hinshelwood-RRK theory, RRKM theory.

11) Photochemistry: absorption, emission, vibrational relaxation, radiationless transitions, collisional. quenching processes, dissociation, photochemical kinetics, quantum yield for fluorescence, the lifetime of an excited state, Stern-Volmer plots, photodissociaion, direct dissociations, stepwise dissociations, predissociation, real time studies of the photodissociation process.

12) Reactions in solution: the encountnir pair, diffusion-controlled reactions, dependence of the rate coefficient for diffusion-controlled reactions on viscosity and temperature, diffusion controlled reactions between ions, the transition to activation-controlled reactions, thermodynamic formulation of the rate coefficient, ionic strength effects, the effect of pressure on the rate coefficient, the dynamics of solution reactions, cage reactions, cluster reactions, the solvated electron, electron transfer reactions.

13) Surface reactions: adsorption on metal surfaces, structural characterization of surface species, the Langmuir adsorption isotherm, dynamics of surface adsorption, kinetics of surface catalysed reactions, unimolecular decomposition, bimolecular reactions.

Remark: This course introduces the fundamentals of chemical dynamics and kinetics on which other classes (e.g. CHEM 507) build. (Contact: D. Luckhaus, Wesbrook W220, phone:827-5650, e-mail:  )