Theoretical investigations of vibrational energy relaxation in solution
Abstract
A rigorous theoretical treatment of vibrational energy relaxation in solution has been developed based on a general theory of dynamics of chemical reactions in solution. Algorithms which permit the construction of a physically realistic generalized Langevin equation of motion for the energy relaxation dynamics of a specified normal mode coordinate immersed at infinite dilution in monatomic and molecular solvent are developed. These algorithms permit the construction, from equilibrium solute-solvent pair correlation functions, of the liquid state frequency of the normal mode, $\omega\sb{l}$, and of the Gaussian model approximation to the autocorrelation function $\langle\tilde{\cal F}(t)\tilde{\cal F}\rangle\sb{o}$ of the fluctuating force exerted by the solvent on the solute normal mode. From these quantities, one may compute the vibration energy relaxation time $T\sb1$ of the solute normal mode and assess the relative importance of the various energy dissipation pathways, solute vibration $\leftrightarrow$ solvent, solute vibration $\leftrightarrow$ solute translation $\leftrightarrow$ solvent, and solute vibration $\leftrightarrow$ solute translation, solute rotation $\leftrightarrow$ solvent. Numerical studies are presented for the prototype case of a diatomic solute in a monatomic solvent along with studies of more chemically interesting systems in molecular solvents. The study of VER in neat $O\sb2$ is presented.
Degree
Ph.D.
Advisors
Adelman, Purdue University.
Subject Area
Chemistry
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