title: Ring polymer molecular dynamics with surface hopping.
abstract: We propose a ring polymer molecular dynamics method for the calculation of chemical rate constants that incorporates nonadiabatic effects by the surface-hopping approach. Two approximate ring polymer electronic Hamiltonians are formulated and the time-dependent Schrodinger equation for the electronic amplitudes is solved self-consistently with the ring polymer equations of motion. The beads of the ring polymer move on a single adiabatic potential energy surface at all times except for instantaneous surface hops. The probability for a hop is determined by the fewest-switches surface-hopping criterion. During a surface hop all beads switch simultaneously to the new potential energy surface with positions kept unchanged and momenta adjusted properly to conserve total energy. The approach allows the evaluation of total rate coefficients as well as electronic state-selected contributions. The method is tested against exact quantum mechanical calculations for a one-dimensional, two-state model system that mimics a prototypical nonadiabatic bimolecular chemical reaction. For this model system, the method reproduces quite accurately the tunneling contribution to the rate and the distribution of reactants between the electronic states.
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
authors.forename: Philip
authors.initials: P
authors.lastname: Shushkov
authors.forename: Richard
authors.initials: R
authors.lastname: Li
authors.forename: John C
authors.initials: JC
authors.lastname: Tully