Quantum Simulation of Chemical Dynamics in Solution

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Peter Rossky of the University of Texas at Austin is supported by the Theoretical and Computational Chemistry Program to carry out research that addresses the development and application of simulation methods to describe nonadiabatic chemical processes in condensed phases, emphasizing electronic processes in liquid environments. The plan includes a balanced approach to the development of methods and the application of these theoretical methods to experimentally studied systems. The project will focus on three areas. First, non-adiabatic electronic dynamics for intramolecular electron transfer will be explored using direct simulation, to investigate intramolecular and solvent dynamical effects on rates, spectroscopy and electronic coupling, the environmental dependence of electronic structure, and the role of non-equilibrium initial conditions. Next, fully detailed two state/harmonic bath models of solvated electrons and of intramolecular charge transfer systems will be developed and implemented, allowing considerably more rigorous validation of reduced descriptions and of theoretical algorithms, as well as enabling new insights into molecular chemical dynamics. Finally, new theory and algorithms will be developed for atomistic non-adiabatic simulation, including alternative descriptions of environmentally induced electronic quantum coherence decay and alternative algorithms for implementing dissipative quantum dynamics simulation. Outcomes from this effort are expected to reveal the mechanistic character of the individual chemical examples of interest, increase the interpretive capacity of model-based descriptions of experimental data, and enhance the predictive capacity of theory and modeling applied to increasingly complex systems.Most chemical processes occur in a condensed liquid or solid, including those reactions that are responsible for biological function and synthetic materials performance. This research project aims to elucidate theoretical principles underlying chemical phenomena that involve changes in electronic state. Continued advances in related experimental methods will make theory and experiment increasingly able to interact directly, and promise to enhance the understanding and predicted capability of models for electroluminescent materials, biological processes such as photosynthesis, and chemical processes that occur in solution phase photochemistry.