Quantum Operator Approaches to Condensed Phase and Multidimensional Reaction Dynamics

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Steven Schwartz of Yeshiva University is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research in quantum operator approaches to condensed phase multidimensional reaction dynamics. Schwartz' approach to the solution of the quantum dynamics of a system in solution is based on a Generalized Langevin Equation using a microscopic Hamiltonian system in which a discrete harmonic bath is bilinearly coupled to a system coordinate. Using an evolution operator expansion and resummation methodologies, Schwartz applies this methodology to the study of reaction coordinates in solvated chemical systems. In addition to extending the methodology to quantum simulations in many dimensional systems involving quantum activated rate theory, Schwartz will apply his operator approach to the following systems of chemical interest: 1) proton transfer from phenol to amine in aprotic, polar solvents; 2) internal proton transfer in glycine dissolved in water; and 3) hydride transfer in alcohol dehydrogenase reaction. Specific questions to be examined include the effect of spatially dependent friction, the temperature dependence of the bath, and the importance of promoting vibrations.A great deal of progress has been made in the theoretical treatment of gas phase chemical reactions of systems consisting of relatively few atoms. Using state-of-the-art theoretical methods, it is now possible to explain a great deal of the experimental detail for such systems. However, the large majority of reactions which are of interest to chemists occur in condensed phase systems in the presence of solvent. The theoretical models for treating such complex systems are in a much earlier stage of development. Schwartz is developing new theoretical approaches for dealing with solvated chemical systems undergoing chemical reactions where quantum effects may be important.