Including quantum decoherence in surface hopping

Abstract

In this paper we set up a method called overlap decoherence correction (ODC) to take into account the quantum decoherence effect in a surface hopping framework. While keeping the standard surface hopping approach based on independent trajectories, our method allows to account for quantum decoherence by evaluating the overlap between frozen Gaussian wavepackets, the time evolution of which is obtained in an approximate way. The ODC scheme mainly depends on the parameter σ, which is the Gaussian width of the wavepackets. The performance of the ODC method is tested versus full quantum calculations on three model systems, and by comparison with full multiple spawning (FMS) results for the S(1)→S(0) decay in the azobenzene molecule.