Theoretical and Computational Chemical Dynamics and Energetics

Donald Truhlar of the University of Minnesota is supported by the Theoretical and Computational Chemistry Program to study electronically nonadiabatic reactive collisions in the gas phase and nonequilibrium solvation effects on liquid phase reaction rates, using methods in theoretical and computational chemical physics. In the treatment of electronically nonadiabatic reactions, issues to be emphasized are: (1) development of accurate quantum mechanical scattering theories to calculate well converged state-to-state reaction probabilities of systems governed by coupled potential energy surfaces, (2) development of new semiclassical methods based on improved treatments of decoherence and continuous surface switching, (3) testing of semiclassical methods against accurate quantum mechanical scattering results for a variety of systems, (4) development of new methods for diabatic representations of coupled electronic wave functions and coupled potential energy surfaces, and (5) use of these methods to study electronically nonadiabatic systems for which experimental data are available. In the treatment of nonequilibrium solvation effects, issues to be emphasized are: (1) delineating the range of applicability of generalized Langevin solvents coordinates for treating organic reactions in solution, and (2) application of new methods to the reactions of diphenylmethyl chloride and bromide.

This research will impact our molecular level understanding of chemical dynamics and solvation, which in turn will have implications in areas such as atmospheric and environmental chemistry.