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

Citation

Mortimer, Robert George (1963) 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. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/6XPY-Y044. https://resolver.caltech.edu/CaltechTHESIS:04302012-143409544

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.

Thesis Files