I. Irreversible Thermodynamics of Systems Containing Radiation. Application to Photochemical Reactions. II. Mean Values in Ensembles of Systems of Particles with Long-Range Potentials. III. Approximations to Time-Dependent Ensemble Averages

Author: Mortimer, Robert George

Year: 1963

Degree: Dissertation (Ph.D.)

Advisor: Mazo, Robert M.

Committee Member: Unknown, Unknown

Option: Chemistry; Physics

DOI: 10.7907/6XPY-Y044

Abstract

I. The general theory of the irreversible thermodynamics of chemically reacting systems interacting with radiation is developed. From this, a limit to the efficiency of photochemical processes is derived, and this is compared with approximate experimental efficiencies of published researches, which are found to be considerably lower.

II. A general cluster method of obtaining approximations to ensemble averages of functions depending on coordinates and/or momenta at a single time is derived, starting with a method, due to Mazo and Zemach, valid only for short-range forces, and proceeding to a method capable of treating systems of particles with long and short-range potentials, such as ionic solutions.

III. Approaches to the time evolution of distribution functions and to time-correlation functions are discussed. A general perturbation series approach to time-correlation functions through the exponential Liouville operator is derived, and this is applied to the calculation of the first-order correction to a Fokker-Planck friction constant and to first and second-order corrections to a momentum autocorrelation function.

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