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Path-integral isomorphic Hamiltonian for including nuclear quantum effects in non-adiabatic dynamics

Tao, Xuecheng and Shushkov, Philip and Miller, Thomas F., III (2018) Path-integral isomorphic Hamiltonian for including nuclear quantum effects in non-adiabatic dynamics. Journal of Chemical Physics, 148 (10). Art. No. 102327. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20171212-125750800

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Abstract

We describe a path-integral approach for including nuclear quantum effects in non-adiabatic chemical dynamics simulations. For a general physical system with multiple electronic energy levels, a corresponding isomorphic Hamiltonian is introduced such that Boltzmann sampling of the isomorphic Hamiltonian with classical nuclear degrees of freedom yields the exact quantum Boltzmann distribution for the original physical system. In the limit of a single electronic energy level, the isomorphic Hamiltonian reduces to the familiar cases of either ring polymer molecular dynamics (RPMD) or centroid molecular dynamics Hamiltonians, depending on the implementation. An advantage of the isomorphic Hamiltonian is that it can easily be combined with existing mixed quantum-classical dynamics methods, such as surface hopping or Ehrenfest dynamics, to enable the simulation of electronically non-adiabatic processes with nuclear quantum effects. We present numerical applications of the isomorphic Hamiltonian to model two- and three-level systems, with encouraging results that include improvement upon a previously reported combination of RPMD with surface hopping in the deep-tunneling regime.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/1.5005544DOIArticle
http://aip.scitation.org/doi/10.1063/1.5005544PublisherArticle
https://arxiv.org/abs/1709.06722arXivDiscussion Paper
ORCID:
AuthorORCID
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2017 Published by AIP Publishing. Received 18 September 2017; accepted 20 November 2017; published online 12 December 2017. We acknowledge support from the Office of Naval Research under Award No. N00014-10-1-0884 and the Air Force Office of Scientific Research under Award No. FA9550-17-1-0102. Additionally, P.S. acknowledges a German Research Foundation (DFG) Postdoctoral Fellowship, and T.F.M. acknowledges a Camille Dreyfus Teacher-Scholar Award. 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.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-10-1-0884
Air Force Office of Scientific Research (AFOSR)FA9550-17-1-0102
Deutsche Forschungsgemeinschaft (DFG)UNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Department of Energy (DOE)DE-AC02-05CH11231
Subject Keywords:Quantum effects; Molecular dynamics; Nuclear structure models; Thermodynamic processes; Transition state theory
Record Number:CaltechAUTHORS:20171212-125750800
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20171212-125750800
Official Citation:Path-integral isomorphic Hamiltonian for including nuclear quantum effects in non-adiabatic dynamics. Xuecheng Tao, Philip Shushkov, and Thomas F. Miller III. The Journal of Chemical Physics 2018 148:10
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:83830
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Dec 2017 21:10
Last Modified:23 Jan 2018 22:38

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