Chemical Physics Letters, Vol.440, No.4-6, 215-220, 2007
Quantum equilibrium structure for strong nonadiabatic coupling: Reaction rate enhancement
The quantum reactive flux correlation function is computed for a two-level system using an expression for the quantum equilibrium structure appropriate for strong nonadiabatic coupling, in conjunction with quantum-classical Liouville dynamics. The magnitude of the quantum mechanical enhancement of the reaction rate as a result of strong nonadiabatic coupling is studied. The reaction rate is found to increase strongly with an increase in the nonadiabatic coupling strength as well as with a decrease in the temperature. Equilibrium quantum effects increase the ground-state contribution to the rate constant but these effects decrease the excited-state contribution. (C) 2007 Elsevier B.V. All rights reserved.