📝 SummarXiv

Abstract

Ring-polymer surface hopping (RPSH) is a unique mixed quantum-classical dynamics method that seamlessly incorporates nuclear quantum effects (NQEs) into non-adiabatic dynamics simulations via the extended phase-space of a classical ring polymer. Here, we systematically investigate several variants of RPSH in the frameworks of centroid and bead approximations (RPSH-CA and RPSH-BA) in modeling the dynamics of the spin-boson system across different reaction regimes, reorganization energies, and temperatures. Moreover, the effects of including the diagonal Born-Oppenheimer correction (DBOC) on the performance of the RPSH-CA and RPSH-BA methods are investigated. Our results show that the RPSH-CA method, where non-adiabatic transitions are handled at the centroid level, reliably captures NQEs and remains robust across different reaction regimes. Adding DBOC improves the method's accuracy in specific intermediate and non-adiabatic reaction regimes at low temperature. Conversely, adding DBOC to the conventional fewest-switches surface hopping method was found to over-damp the dynamics significantly and reduce accuracy, especially at low temperatures. On the other hand, RPSH-BA results, where non-adiabatic transitions are handled at the level of individual beads of the ring polymers, are generally unreliable unless in the adiabatic reaction regime and at high temperature. The inclusion of DBOC is not particularly helpful in remedying this erratic behavior. As such, RPSH-BA is not recommended for including NQEs in condensed-phase non-adiabatic dynamics simulations despite its early successful reports in 1D scattering models. Our findings clarify when geometric corrections are beneficial or detrimental to non-adiabatic simulations using RPSH, providing practical guidance for atomistic condensed-phase applications.