A comparison of surface hopping approaches for capturing metal-molecule electron transfer: A broadened classical master equation versus independent electron surface hopping

Abstract

The symmetrical quasi-classical approach to electronically nonadiabatic dynamics applied to ultrafast exciton migration processes in semiconducting polymers

Configuration interaction approaches for solving quantum impurity models

“…relies on an independent electrons and cannot directly include electron-electron repulsion (as would be found in a realistic ab initio Hamiltonian); finite temperature effects are also difficult [66].…”

“…For this reason, Shenvi et al [64] originally developed the independent electron surface hopping model. Nevertheless, for all of its successes [65], the IESH model relies on an independent electrons and cannot directly include electron-electron repulsion (as would be found in a realistic ab initio Hamiltonian); finite temperature effects are also difficult [66].…”

Nonadiabatic Molecular Dynamics at Metal Surfaces

“…To make the computational cost affordable while still treating many electronic states, the Hamiltonian models independent electrons such that the electronic wave function is always the simple product of one-electron orbitals. In practice, the IESH algorithm is a powerful approach for simulating dynamics at surfaces, , and we have recently demonstrated that IESH does agree with Marcus theory under the right conditions . The only hiccup with IESH is that, for gas-phase scattering calculations (i.e., without a nuclear bath), there is no natural means to include electronic relaxation of the Fermi sea bath to the Fermi level without introducing artifacts; this remains an outstanding question for future development.…”

Nonadiabatic dynamics at metal surfaces: fewest switches surface hopping with electronic relaxation

“…A second approach to this same problem is the broadened classical master equation (BCME), 27,89 which was recently developed by our research group and compared with IESH. 90 BCME extrapolates the CME to the strong molecular-metal coupling regime (Γ > kT ). The BCME yields accurate and efficient results for the Anderson-Holstein model 90,91 and has been recently applied to electrochemical model problems.…”

“…90 BCME extrapolates the CME to the strong molecular-metal coupling regime (Γ > kT ). The BCME yields accurate and efficient results for the Anderson-Holstein model 90,91 and has been recently applied to electrochemical model problems. 92 However, at bottom, the BCME method is formulated in a (modified) molecular diabatic picture, which has both upsides and downsides.…”