Consistent Construction of the Density Matrix from Surface Hopping Trajectories.

Abstract

Proper construction of the density matrix based on surface hopping trajectories remains a difficult problem. Due to the well-known overcoherence in traditional surface hopping simulations, the electronic wave function cannot be used directly. In this work, we propose a consistent density matrix construction method, which takes the advantage of occupation of active states to rescale the coherence calculated by wave functions and ensures the intrinsic consistency of the density matrix. This new trajectory analysis method can be used for both Tully's fewest switches surface hopping (FSSH) and our recently proposed branching corrected surface hopping (BCSH). As benchmarked in both one- and two-dimensional standard scattering models, the new approach combined with BCSH trajectories achieves highly accurate time-dependent spatial distributions of adiabatic populations and coherence compared to exact quantum results.