A new approach to decoherence and momentum rescaling in the surface hopping algorithm.
As originally proposed, the fewest switches surface hopping (FSSH) algorithm does not allow for decoherence between wavefunction amplitudes on different adiabatic surfaces. In this paper, we propose an inexpensive correction to standard FSSH dynamics wherein we explicitly model the decoherence of nuclear wave packets on distinct electronic surfaces. Our augmented fewest switches surface hopping approach is conceptually simple and, thus far, it has allowed us to capture several key features of the exact quantum results. Two points in particular merit attention. First, we obtain the correct branching ratios when a quantum particle passes through more than one region of nonadiabatic coupling. Second, our formalism provides a new and natural approach for rescaling nuclear momenta after a surface hop. Both of these features should become increasingly important as surface hopping schemes are applied to higher-dimensional problems.
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA. subotnik@sas.upenn.edu
Joseph E
JE
Subotnik
Neil
N
Shenvi
D000465:Algorithms; D011789:Quantum Theory; D013499:Surface Properties