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Title: Kinetically-constrained ring-polymer molecular dynamics for non-adiabatic chemistries involving solvent and donor–acceptor dynamical effects

Abstract

We investigate the performance of the recently developed kinetically-constrained ring polymer molecular dynamics (KC-RPMD) method for the description of model condensed-phase electron transfer (ET) reactions in which solvent and donor–acceptor dynamics play an important role. Comparison of KC-RPMD with results from Golden-Rule rate theories and numerically exact quantum dynamics calculations demonstrates that KC-RPMD accurately captures the combination of electronic- and nuclear-dynamical effects throughout the Marcus (intermediate solvent friction) and Zusman (large solvent friction) regimes of ET. It is also demonstrated that KC-RPMD accurately describes systems in which the magnitude of the diabatic coupling depends on the position of a dynamical donor–acceptor mode. In addition to these successes, however, we present an unsurprising failure of KC-RPMD to capture the enhancement of the ET rate in the low solvent friction regime associated with nuclear coherence effects. In this analysis, we re-visit several aspects of the original KC-RPMD formulation, including the form of the kinetic constraint and the choice of the mass of the auxiliary electronic variable. In particular, we introduce a Langevin bath for the auxiliary electronic variable to correct for its unphysically low coupling with the nuclear degrees of freedom. This work demonstrates that the KC-RPMD method is well suited formore » the direct simulation of non-adiabatic donor–acceptor chemistries associated with many complex systems, including those for which solvent dynamics plays an important role in the reaction mechanism.« less

Authors:
 [1];  [1]
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  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1491825
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 195; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kretchmer, Joshua S., and Miller III, Thomas F. Kinetically-constrained ring-polymer molecular dynamics for non-adiabatic chemistries involving solvent and donor–acceptor dynamical effects. United States: N. p., 2016. Web. doi:10.1039/c6fd00143b.
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Kretchmer, Joshua S., & Miller III, Thomas F. Kinetically-constrained ring-polymer molecular dynamics for non-adiabatic chemistries involving solvent and donor–acceptor dynamical effects. United States. https://doi.org/10.1039/c6fd00143b
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Kretchmer, Joshua S., and Miller III, Thomas F. Thu . "Kinetically-constrained ring-polymer molecular dynamics for non-adiabatic chemistries involving solvent and donor–acceptor dynamical effects". United States. https://doi.org/10.1039/c6fd00143b. https://www.osti.gov/servlets/purl/1491825.
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@article{osti_1491825,
title = {Kinetically-constrained ring-polymer molecular dynamics for non-adiabatic chemistries involving solvent and donor–acceptor dynamical effects},
author = {Kretchmer, Joshua S. and Miller III, Thomas F.},
abstractNote = {We investigate the performance of the recently developed kinetically-constrained ring polymer molecular dynamics (KC-RPMD) method for the description of model condensed-phase electron transfer (ET) reactions in which solvent and donor–acceptor dynamics play an important role. Comparison of KC-RPMD with results from Golden-Rule rate theories and numerically exact quantum dynamics calculations demonstrates that KC-RPMD accurately captures the combination of electronic- and nuclear-dynamical effects throughout the Marcus (intermediate solvent friction) and Zusman (large solvent friction) regimes of ET. It is also demonstrated that KC-RPMD accurately describes systems in which the magnitude of the diabatic coupling depends on the position of a dynamical donor–acceptor mode. In addition to these successes, however, we present an unsurprising failure of KC-RPMD to capture the enhancement of the ET rate in the low solvent friction regime associated with nuclear coherence effects. In this analysis, we re-visit several aspects of the original KC-RPMD formulation, including the form of the kinetic constraint and the choice of the mass of the auxiliary electronic variable. In particular, we introduce a Langevin bath for the auxiliary electronic variable to correct for its unphysically low coupling with the nuclear degrees of freedom. This work demonstrates that the KC-RPMD method is well suited for the direct simulation of non-adiabatic donor–acceptor chemistries associated with many complex systems, including those for which solvent dynamics plays an important role in the reaction mechanism.},
doi = {10.1039/c6fd00143b},
journal = {Faraday Discussions},
number = ,
volume = 195,
place = {United States},
year = {Thu Jun 23 00:00:00 EDT 2016},
month = {Thu Jun 23 00:00:00 EDT 2016}
}
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https://doi.org/10.1039/c6fd00143b
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Cited by: 23 works
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Table 1 Table 1: Parameters for system Aa
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Works referenced in this record:

Communication: Relation of centroid molecular dynamics and ring-polymer molecular dynamics to exact quantum dynamics
journal, May 2015

  • Hele, Timothy J. H.; Willatt, Michael J.; Muolo, Andrea
  • The Journal of Chemical Physics, Vol. 142, Issue 19
  • DOI: 10.1063/1.4921234

A classical analog for electronic degrees of freedom in nonadiabatic collision processes
journal, April 1979

  • Meyera), Hans‐Dieter; Miller, William H.
  • The Journal of Chemical Physics, Vol. 70, Issue 7
  • DOI: 10.1063/1.437910

Path Integral Calculation of Quantum Nonadiabatic Rates in Model Condensed Phase Reactions
journal, January 1996

  • Topaler, Maria; Makri, Nancy
  • The Journal of Physical Chemistry, Vol. 100, Issue 11
  • DOI: 10.1021/jp951673k

Outer-sphere electron transfer in polar solvents
journal, July 1980

Ring polymer molecular dynamics beyond the linear response regime: Excess electron injection and trapping in liquids
journal, January 2010

  • Menzeleev, Artur R.; Miller, Thomas F.
  • The Journal of Chemical Physics, Vol. 132, Issue 3
  • DOI: 10.1063/1.3292576

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 24, Issue 5
  • DOI: 10.1063/1.1742723

Second-order integrators for Langevin equations with holonomic constraints
journal, September 2006

Electron transfers in chemistry and biology
journal, August 1985

  • Marcus, R. A.; Sutin, Norman
  • Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3
  • DOI: 10.1016/0304-4173(85)90014-X

Multidimensional free-energy calculations using the weighted histogram analysis method
journal, November 1995

  • Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal
  • Journal of Computational Chemistry, Vol. 16, Issue 11
  • DOI: 10.1002/jcc.540161104

Outer-sphere electron-transfer reactions and frequency-dependent friction
journal, July 1986

  • Hynes, James T.
  • The Journal of Physical Chemistry, Vol. 90, Issue 16
  • DOI: 10.1021/j100407a044

Mapping variable ring polymer molecular dynamics: A path-integral based method for nonadiabatic processes
journal, September 2013

  • Ananth, Nandini
  • The Journal of Chemical Physics, Vol. 139, Issue 12
  • DOI: 10.1063/1.4821590

Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics
journal, October 2013

  • Huo, Pengfei; Miller, Thomas F.; Coker, David F.
  • The Journal of Chemical Physics, Vol. 139, Issue 15
  • DOI: 10.1063/1.4826163

Semiclassical approximations for the calculation of thermal rate constants for chemical reactions in complex molecular systems
journal, June 1998

  • Wang, Haobin; Sun, Xiong; Miller, William H.
  • The Journal of Chemical Physics, Vol. 108, Issue 23
  • DOI: 10.1063/1.476447

Direct simulation of proton-coupled electron transfer across multiple regimes
journal, April 2013

  • Kretchmer, Joshua S.; Miller, Thomas F.
  • The Journal of Chemical Physics, Vol. 138, Issue 13
  • DOI: 10.1063/1.4797462

Classical and quantum pictures of reaction dynamics in condensed matter: resonances, dephasing, and all that
journal, November 1988

  • Onuchic, Jose Nelson; Wolynes, Peter G.
  • The Journal of Physical Chemistry, Vol. 92, Issue 23
  • DOI: 10.1021/j100334a007

Tipping the Balance between Concerted versus Sequential Proton-Coupled Electron Transfer
journal, October 2015

Mixed quantum–classical dynamics
journal, January 1998

Classical path surface‐hopping dynamics. I. General theory and illustrative trajectories
journal, July 1991

  • Kuntz, P. J.
  • The Journal of Chemical Physics, Vol. 95, Issue 1
  • DOI: 10.1063/1.461470

Infrared photodissociation spectroscopy of protonated ammonia cluster ions, NH4+(NH3)n (n=5–8), by using infrared free electron laser
journal, December 2006

  • Tono, Kensuke; Bito, Kotatsu; Kondoh, Hiroshi
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404671

Ring-Polymer Molecular Dynamics: Quantum Effects in Chemical Dynamics from Classical Trajectories in an Extended Phase Space
journal, April 2013

Ring-polymer instanton theory of electron transfer in the nonadiabatic limit
journal, October 2015

  • Richardson, Jeremy O.
  • The Journal of Chemical Physics, Vol. 143, Issue 13
  • DOI: 10.1063/1.4932362

A unified framework for quantum activated rate processes. I. General theory
journal, October 1996

  • Cao, Jianshu; Voth, Gregory A.
  • The Journal of Chemical Physics, Vol. 105, Issue 16
  • DOI: 10.1063/1.471980

Charge and Energy Transfer Dynamics in Molecular Systems
book, February 2011

Long-range electron transfer
journal, February 2005

  • Gray, H. B.; Winkler, J. R.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 10
  • DOI: 10.1073/pnas.0408029102

Statistical mechanics of isomerization dynamics in liquids and the transition state approximation
journal, January 1978

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 68, Issue 6
  • DOI: 10.1063/1.436049

Time-Sliced Thawed Gaussian Propagation Method for Simulations of Quantum Dynamics
journal, February 2016

  • Kong, Xiangmeng; Markmann, Andreas; Batista, Victor S.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 19
  • DOI: 10.1021/acs.jpca.5b12192

Nonadiabatic Trajectories at an Exhibition
journal, August 2000

  • Hack, Michael D.; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 34
  • DOI: 10.1021/jp001629r

Quantum rates for a double well coupled to a dissipative bath: Accurate path integral results and comparison with approximate theories
journal, November 1994

  • Topaler, Maria; Makri, Nancy
  • The Journal of Chemical Physics, Vol. 101, Issue 9
  • DOI: 10.1063/1.468244

Quantum statistics and classical mechanics: Real time correlation functions from ring polymer molecular dynamics
journal, August 2004

  • Craig, Ian R.; Manolopoulos, David E.
  • The Journal of Chemical Physics, Vol. 121, Issue 8
  • DOI: 10.1063/1.1777575

Calculation of the transition state theory rate constant for a general reaction coordinate: Application to hydride transfer in an enzyme
journal, January 2006

THE weighted histogram analysis method for free-energy calculations on biomolecules. I. The method
journal, October 1992

  • Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130812

A self‐consistent eikonal treatment of electronic transitions in molecular collisions
journal, June 1983

  • Micha, D. A.
  • The Journal of Chemical Physics, Vol. 78, Issue 12
  • DOI: 10.1063/1.444753

A unified framework for quantum activated rate processes. II. The nonadiabatic limit
journal, February 1997

  • Cao, Jianshu; Voth, Gregory A.
  • The Journal of Chemical Physics, Vol. 106, Issue 5
  • DOI: 10.1063/1.474123

Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods
journal, August 2011

  • Menzeleev, Artur R.; Ananth, Nandini; Miller, Thomas F.
  • The Journal of Chemical Physics, Vol. 135, Issue 7
  • DOI: 10.1063/1.3624766

Isomorphic classical molecular dynamics model for an excess electron in a supercritical fluid
journal, November 2008

  • Miller, Thomas F.
  • The Journal of Chemical Physics, Vol. 129, Issue 19
  • DOI: 10.1063/1.3013357

Iterative linearized density matrix propagation for modeling coherent excitation energy transfer in photosynthetic light harvesting
journal, November 2010

  • Huo, P.; Coker, D. F.
  • The Journal of Chemical Physics, Vol. 133, Issue 18
  • DOI: 10.1063/1.3498901

On the equivalence of two commonly used forms of semiclassical instanton theory
journal, March 2011

  • Althorpe, Stuart C.
  • The Journal of Chemical Physics, Vol. 134, Issue 11
  • DOI: 10.1063/1.3563045

Generalized transition state theory in terms of the potential of mean force
journal, September 2003

  • Schenter, Gregory K.; Garrett, Bruce C.; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 119, Issue 12
  • DOI: 10.1063/1.1597477

Dynamic solvent effects on outer‐sphere electron transfer
journal, August 1987

  • Rips, Ilya; Jortner, Joshua
  • The Journal of Chemical Physics, Vol. 87, Issue 4
  • DOI: 10.1063/1.453184

The Activated Complex in Chemical Reactions
journal, February 1935

  • Eyring, Henry
  • The Journal of Chemical Physics, Vol. 3, Issue 2
  • DOI: 10.1063/1.1749604

The transition from nonadiabatic to solvent controlled adiabatic electron transfer: Solvent dynamical effects in the inverted regime
journal, July 1989

  • Yang, D. Y.; Cukier, R. I.
  • The Journal of Chemical Physics, Vol. 91, Issue 1
  • DOI: 10.1063/1.457514

How to remove the spurious resonances from ring polymer molecular dynamics
journal, June 2014

  • Rossi, Mariana; Ceriotti, Michele; Manolopoulos, David E.
  • The Journal of Chemical Physics, Vol. 140, Issue 23
  • DOI: 10.1063/1.4883861

The calculation of the potential of mean force using computer simulations
journal, September 1995

Symmetrical Windowing for Quantum States in Quasi-Classical Trajectory Simulations
journal, March 2013

  • Cotton, Stephen J.; Miller, William H.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 32
  • DOI: 10.1021/jp401078u

Effect of friction on electron transfer in biomolecules
journal, November 1985

  • Garg, Anupam; Onuchic, José Nelson; Ambegaokar, Vinay
  • The Journal of Chemical Physics, Vol. 83, Issue 9
  • DOI: 10.1063/1.449017

Bemerkung �ber die angen�herte G�ltigkeit der klassischen Mechanik innerhalb der Quantenmechanik
journal, July 1927

Molecular dynamics with electronic transitions
journal, July 1990

  • Tully, John C.
  • The Journal of Chemical Physics, Vol. 93, Issue 2
  • DOI: 10.1063/1.459170

Simulating Excited State Dynamics in Systems with Multiple Avoided Crossings Using Mapping Variable Ring Polymer Molecular Dynamics
journal, October 2015

On the connection of semiclassical instanton theory with Marcus theory for electron transfer in solution
journal, June 2013

  • Shushkov, Philip
  • The Journal of Chemical Physics, Vol. 138, Issue 22
  • DOI: 10.1063/1.4807706

Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions
journal, February 2014

  • Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F.
  • The Journal of Chemical Physics, Vol. 140, Issue 6
  • DOI: 10.1063/1.4863919

Variational Theory of Chemical Reaction Rates Applied to Three‐Body Recombinations
journal, April 1960

  • Keck, James C.
  • The Journal of Chemical Physics, Vol. 32, Issue 4
  • DOI: 10.1063/1.1730846

Chemical reaction rates from ring polymer molecular dynamics
journal, February 2005

  • Craig, Ian R.; Manolopoulos, David E.
  • The Journal of Chemical Physics, Vol. 122, Issue 8
  • DOI: 10.1063/1.1850093

Theory of Electron‐Transfer Reaction Rates of Solvated Electrons
journal, November 1965

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 43, Issue 10
  • DOI: 10.1063/1.1696504

Semiclassical theory of electronically nonadiabatic dynamics: Results of a linearized approximation to the initial value representation
journal, November 1998

  • Sun, Xiong; Wang, Haobin; Miller, William H.
  • The Journal of Chemical Physics, Vol. 109, Issue 17
  • DOI: 10.1063/1.477389

Derivation of instanton rate theory from first principles
journal, March 2016

  • Richardson, Jeremy O.
  • The Journal of Chemical Physics, Vol. 144, Issue 11
  • DOI: 10.1063/1.4943866

Kinetically Constrained Ring-Polymer Molecular Dynamics for Non-adiabatic Chemical Reactions
text, January 2014

How to remove the spurious resonances from ring polymer molecular dynamics
text, January 2014

Derivation of instanton rate theory from first principles
text, January 2015

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    journal, March 2018

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    • DOI: 10.1073/pnas.1805719115

    Instanton formulation of Fermi’s golden rule in the Marcus inverted regime
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    Instanton formulation of Fermi's golden rule in the Marcus inverted regime
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