Mixed quantum-classical equilibrium: Surface hopping.
We re-examine the analysis of the equilibrium limits of the fewest switches surface hopping algorithm for mixed quantum-classical dynamics. In contrast with previously reported results, we show that surface hopping does not, in general, exactly yield Boltzmann equilibrium, but that in practice the observed deviations are quite small. We also demonstrate that surface hopping does approach the exact equilibrium distribution in both the limits of small adiabatic splitting and/or strong nonadiabatic coupling. We verify these analytical results with numerical simulations for a simple two-level quantum system connected to a bath of classical particles.
Schmidt
J R
JR
Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
Parandekar
Priya V
PV
Tully
John C
JC