Detailed Balance and Independent Electron Surface-Hopping Method: The Importance of Decoherence and Correct Calculation of Diabatic Populations

We benchmark and improve the independent electron surface-hopping (IESH) method developed by J. C. Tully’s group for nonadiabatic simulations near metal surfaces. We have incorporated decoherence within the IESH method as well as implemented a scheme for the accurate calculation of diabatic populations. We benchmark the original IESH method with the above inclusions for a model system to calculate rate constants and long-time populations. The original IESH method fails to capture the detailed balance for some of the parameters, which is corrected with the inclusion of decoherence and accurate calculation of diabatic populations. Total rate constants are well captured both within the original IESH method as well as within our modified IESH.