A comparison of surface hopping approaches for capturing metal-molecule electron transfer: A broadened classical...

Within a generalized Anderson-Holstein model, we investigate electron transfer rates using two different surface hopping algorithms: a broadened classical master equation (BCME) and independent electron surface hopping (IESH). We find that for large enough bandwidth and density of one electron states, and in the presence of external friction, the IESH results converge to the BCME results for impurity-bath model systems, recovering both relaxation rates and equilibrium populations. Without external friction, however, the BCME and IESH results can strongly disagree, and preliminary evidence suggests that IESH does not always recover the correct equilibrium state. Finally, we also demonstrate that adding an electronic thermostat to IESH does help drive the metallic substrate to the correct equilibrium state, but this improvement can sometimes come at the cost of worse short time dynamics. Overall, our results should be of use for all computational chemists looking to model either gas phase scattering or electrochemical dynamics at a metal interface.