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Published March 14, 2018 | Published + Submitted
Journal Article Open

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

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.

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.

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Published - 1.5005544.pdf

Submitted - 1709.06722.pdf

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Additional details

Created:
August 21, 2023
Modified:
October 17, 2023