A Simple Flux-Side Formulation of State-Resolved Thermal Reaction Rates for Ring-Polymer Surface Hopping
Abstract
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.
Additional Information
© 2019 American Chemical Society. Received: January 29, 2019; Revised: February 22, 2019; Published: February 22, 2019. We acknowledge support from the Office of Naval Research under Award Number N00014-10-1-0884. Additionally, P.S. acknowledges a German Research Foundation (DFG) Postdoctoral Fellowship. Computational resources were provided by the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors declare no competing financial interest.Additional details
- Eprint ID
- 93223
- Resolver ID
- CaltechAUTHORS:20190225-105719386
- N00014-10-1-0884
- Office of Naval Research (ONR)
- Deutsche Forschungsgemeinschaft (DFG)
- DE-AC02-05CH11231
- Department of Energy (DOE)
- Created
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2019-02-25Created from EPrint's datestamp field
- Updated
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2021-11-16Created from EPrint's last_modified field