Tao Xuecheng, Shushkov Philip, Miller Thomas F
Division of Chemistry and Chemical Engineering , California Institute of Technology , Pasadena , California 91125 , United States.
J Phys Chem A. 2019 Apr 4;123(13):3013-3020. doi: 10.1021/acs.jpca.9b00877. Epub 2019 Mar 21.
Employing the recently developed isomorphic Hamiltonian framework for including nuclear quantum effects in mixed quantum-classical nonadiabatic dynamics, we present a flux-side formulation of state-resolved thermal reaction rates for ring-polymer surface hopping (iso-RPSH). An appealing aspect of the new approach is that calculation of multiple state-resolved nonadiabatic thermal reaction rates is enabled with only a single free-energy surface calculation, whereas previous nonadiabatic flux-side formulations for surface hopping involve multiple free-energy surface calculations. The method is shown to be robust and straightforwardly implemented, and numerical results reveal that RPSH in the isomorphic Hamiltonian framework leads to better dividing surface independence than alternative RPSH methods due to improved preservation of the path-integral statistics.
