The Theoretical and Compuational Chemistry Program of the Chemistry Division will support Kellman in a series of theoretical analyses of the dynamics of highly excited rotation-vibration spectra of polyatomic molecules. The work will concentrate in three areas: (1) dynamics of strongly coupled vibrations from experimental spectra, investigating the relation of spectral patterns to phase space structure including low-frequency modes, and phase space structure and bond selective reactivity, (2) work with chaotic systems with many degrees of freedom including search for dynamical constants of motion and quantum number assignments, and phase space bifurcation structure and catastrophe maps for chaotic systems, and (3) determination of molecular potential surfaces from "bootstrap" fitting of highly excited spectra. %%% Modern laser experiments can deposit a large amount of energy in molecules, converting them into highly excited states which are not easily, if at all, describable in the terms that chemists and physicists have used so successfully for matter in or near its ground, most relaxed state. Kellman is developing analytical tools to interpret such experiments and the highly complex or chaotic states that they produce. There are possible practical consequences in terms of the use of laser excitation to affect selected bonds in a molecule, but the principle purpose is to understand more fully the nature of highly excited molecular matter.
