Velocity Adjustment in Surface Hopping: Ethylene as a Case Study of the Maximum Error Caused by Direction Choice

The most common surface hopping dynamics algorithms require velocity adjustment after hopping to ensure total-energy conservation. Based on the semi-classical analysis, this adjustment must be made parallel to the nonadiabatic coupling vector's direction. Nevertheless, this direction is not always known, and the common practice has been to adjust the velocity in either the linear momentum or velocity directions. This paper benchmarks surface hopping dynamics of photoexcited ethylene with velocity adjustment in several directions, including those of the nonadiabatic coupling vector, the momentum, and the energy gradient difference. It is shown that differences in time constants and structural evolution fall within the statistical uncertainty of the method considering up to 500 trajectories in each dynamics set, rendering the three approaches statistically equivalent. For larger ensembles beyond 1000 trajectories, significant differences between the results arise, limiting the validity of adjustment in alternative directions. Other possible adjustment directions (velocity, single-state gradients, angular momentum) are evaluated as well. Given the small size of ethylene, the results reported in this paper should be considered an upper limit for the error caused by the choice of the velocity-adjustment direction on surface hopping dynamics.

Automated summary

This paper benchmarks surface hopping dynamics of photoexcited ethylene with velocity adjustment in several directions and finds that significant differences between the results arise with larger ensembles beyond 1000 trajectories, limiting the validity of adjustment in alternative directions. Other possible adjustment directions are evaluated as well.