Surface hopping in laser-driven molecular dynamics

A theoretical justification of the empirical surface hopping method for the laser-driven molecular dynamics is given by utilizing the formalism of the exact factorization of the molecular wave function [Abedi, Phys. Rev. Lett. 105, 123002 (2010)PRLTAO0031-900710.1103/PhysRevLett.105.123002] in its quantum-classical limit. Employing an exactly solvable H2+-like model system, it is shown that the deterministic classical nuclear motion on a single time-dependent surface in this approach describes the same physics as stochastic (hopping-induced) motion on several surfaces, provided Floquet surfaces are applied. Both quantum-classical methods do describe reasonably well the exact nuclear wave-packet dynamics for extremely different dissociation scenarios. Hopping schemes using Born-Oppenheimer surfaces or instantaneous Born-Oppenheimer surfaces fail completely.