With this grant in the Computational and Theoretical Chemistry Program of the Chemistry Division, Professor Skodje will study the classical nonlinear dynamics of bi-molecular and uni-molecular reactions. The work is at a fundamental level with its goal being to understand basic dynamical effects of importance in predicting the rates of chemical reactions. The role of classical phase space structure will be emphasized and the nature of reactive transport in phase space will be investigated using a new theory for complex decay rates, which is based on recent advances in the theory of strange attractors and repellers, and gives a systematically improvable method to calculate rates. The theory will be especially useful in the study of transient species which have extremely short life times, roughly comparable to the intra-molecular relaxation times. A quantum phase space hydrodynamic model will be applied to the problem of multi-dimensional reactive tunneling. The multi-dimensional tunneling path will be found directly by following the fluid orbits. Also, the notion will be explored that quantum chaos can be regarded as turbulence in the quantum fluid dynamics. Finally, the role of localization in intra-molecular vibrational redistribution and in reaction dynamics will be explored by means of quantum maps. Quantum maps for reactive problems will be used to determine whether localization will suppress (or sometimes promote) chemical reaction.
