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Title: Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4863919· OSTI ID:1565171
 [1];  [1];  [1]
  1. California Inst. of Technology, Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
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In this study, we extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.

Research Organization:
California Institute of Technology (CalTech), Pasadena, CA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231; AC05-00OR22725; SC0006598
OSTI ID:
1565171
Journal Information:
Journal of Chemical Physics, Vol. 140, Issue 6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 87 works
Citation information provided by
Web of Science

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A mapping variable ring polymer molecular dynamics study of condensed phase proton-coupled electron transfer journal December 2017
Perspective: Ring-polymer instanton theory text January 2018
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Nonadiabatic quantum transition-state theory in the golden-rule limit: II. Overcoming the pitfalls of the saddle-pointand semiclassical approximations text January 2019
Probing photodissociation dynamics using ring polymer molecular dynamics text January 2019
How to remove the spurious resonances from ring polymer molecular dynamics journal June 2014
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Instanton formulation of Fermi’s golden rule in the Marcus inverted regime text January 2020
A mapping variable ring polymer molecular dynamics study of condensed phase proton-coupled electron transfer. text January 2017
Non-equilibrium dynamics from RPMD and CMD text January 2016
Probing photodissociation dynamics using ring polymer molecular dynamics journal March 2019
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Coherent state mapping ring polymer molecular dynamics for non-adiabatic quantum propagations journal December 2017
Direct simulation of electron transfer in the cobalt hexammine( ii / iii ) self-exchange reaction journal January 2016
Path integral Liouville dynamics for thermal equilibrium systems journal June 2014
Perspective: Ring-polymer instanton theory journal May 2018
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Dynamically consistent method for mixed quantum-classical simulations: A semiclassical approach journal May 2015
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On the calculation of quantum mechanical electron transfer rates journal September 2019
Path-integral isomorphic Hamiltonian for including nuclear quantum effects in non-adiabatic dynamics journal March 2018
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Accelerated sampling by infinite swapping of path integral molecular dynamics with surface hopping journal February 2018
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Instanton formulation of Fermi’s golden rule in the Marcus inverted regime journal January 2020
Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations journal December 2019
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Studying rare nonadiabatic dynamics with transition path sampling quantum jump trajectories text January 2018
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Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations text January 2019
Instanton formulation of Fermi's golden rule in the Marcus inverted regime text January 2019

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