Quantum Reaction-Rate Simulations

This project will build on recent developments we have made in relating quantum rate theory to practical simulation methods via the development of a rigorous quantum transition-state theory. Initially, the student will get up to speed learning quantum and classical rate theory, and will become proficient at quantum simulation methods such as ring-polymer molecular dynamics. She will then develop a theory to investigate the extent to which ring-polymer molecular dynamics can treat barrierless reactions. The theory is likely to be based on developing a double version of quantum transition-state theory which resembles a quantum version of classical capture theory. After that, she is likely to develop methods for predicting the effects of recrossing on quantum transition-state theory rates and making a link with instanton theory. This project is likely to result in new and practical simulation methods for computing quantum effects in chemical reactions, as well as a better understanding of the quantum theory that underpins such methods. Systems treated are likely to range from gas-phase capture reactions of interest to astrophysics and atmospheric science to condensed phase proton and coupled electron-proton transfer reactions.