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Quantum-classical Liouville dynamics of nonadiabatic proton transfer.

ABSTRACT

A proton transfer reaction in a linear hydrogen-bonded complex dissolved in a polar solvent is studied using mixed quantum-classical Liouville dynamics. In this system, the proton is treated quantum mechanically and the remainder of the degrees of freedom is treated classically. The rates and mechanisms of the reaction are investigated using both adiabatic and nonadiabatic molecular dynamics. We use a nonadiabatic dynamics algorithm which allows the system to evolve on single adiabatic surfaces and on coherently coupled pairs of adiabatic surfaces. Reactive-flux correlation function expressions are used to compute the rate coefficients and the role of the dynamics on the coherently coupled surfaces is elucidated.