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Title: Nonadiabatic Dynamics in Atomistic Environments: Harnessing Quantum-Classical Theory with Generalized Quantum Master Equations

Abstract

The development of methods that can efficiently and accurately treat nonadiabatic dynamics in quantum systems coupled to arbitrary atomistic environments remains a significant challenge in problems ranging from exciton transport in photovoltaic materials to electron and proton transfer in catalysis. Here we show that our recently introduced MF-GQME approach, which combines Ehrenfest mean field theory with the generalized quantum master equation framework, is able to yield quantitative accuracy over a wide range of charge-transfer regimes in fully atomistic environments. This is accompanied by computational speed-ups of up to 3 orders of magnitude over a direct application of Ehrenfest theory. Here, this development offers the opportunity to efficiently investigate the atomistic details of nonadiabatic quantum relaxation processes in regimes where obtaining accurate results has previously been elusive.

Authors:
 [1];  [1];  [1]
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  1. Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1526756
Grant/Contract Number:  
SC0014437
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 23; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; excited state dynamics; electron transfer

Citation Formats

Pfalzgraff, William C., Kelly, Aaron, and Markland, Thomas E. Nonadiabatic Dynamics in Atomistic Environments: Harnessing Quantum-Classical Theory with Generalized Quantum Master Equations. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b02131.
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Pfalzgraff, William C., Kelly, Aaron, & Markland, Thomas E. Nonadiabatic Dynamics in Atomistic Environments: Harnessing Quantum-Classical Theory with Generalized Quantum Master Equations. United States. https://doi.org/10.1021/acs.jpclett.5b02131
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Pfalzgraff, William C., Kelly, Aaron, and Markland, Thomas E. Thu . "Nonadiabatic Dynamics in Atomistic Environments: Harnessing Quantum-Classical Theory with Generalized Quantum Master Equations". United States. https://doi.org/10.1021/acs.jpclett.5b02131. https://www.osti.gov/servlets/purl/1526756.
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@article{osti_1526756,
title = {Nonadiabatic Dynamics in Atomistic Environments: Harnessing Quantum-Classical Theory with Generalized Quantum Master Equations},
author = {Pfalzgraff, William C. and Kelly, Aaron and Markland, Thomas E.},
abstractNote = {The development of methods that can efficiently and accurately treat nonadiabatic dynamics in quantum systems coupled to arbitrary atomistic environments remains a significant challenge in problems ranging from exciton transport in photovoltaic materials to electron and proton transfer in catalysis. Here we show that our recently introduced MF-GQME approach, which combines Ehrenfest mean field theory with the generalized quantum master equation framework, is able to yield quantitative accuracy over a wide range of charge-transfer regimes in fully atomistic environments. This is accompanied by computational speed-ups of up to 3 orders of magnitude over a direct application of Ehrenfest theory. Here, this development offers the opportunity to efficiently investigate the atomistic details of nonadiabatic quantum relaxation processes in regimes where obtaining accurate results has previously been elusive.},
doi = {10.1021/acs.jpclett.5b02131},
journal = {Journal of Physical Chemistry Letters},
number = 23,
volume = 6,
place = {United States},
year = {Thu Nov 12 00:00:00 EST 2015},
month = {Thu Nov 12 00:00:00 EST 2015}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.5b02131
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Cited by: 27 works
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Figures / Tables:

Figure 1 Figure 1: Population dynamics in a regime of strong energetic bias, $ϵ$ = 9.2325 kcal/mol, and weak electronic coupling, $∆$ = 0.01 kcal/mol. The direct Ehrenfest and MF-GQME results are from this work. For comparison, the FSSH population dynamics are from Ref.,32 and the Rips-Jortner result is calculated from Eq.more » 6. Because of the extreme computational cost of converging direct Ehrenfest and FSSH dynamics in this regime, the long time population dynamics for those methods are an exponential fit to the short time data.« less
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Works referenced in this record:

Influence of Site-Dependent Pigment–Protein Interactions on Excitation Energy Transfer in Photosynthetic Light Harvesting
journal, April 2013

  • Rivera, Eva; Montemayor, Daniel; Masia, Marco
  • The Journal of Physical Chemistry B, Vol. 117, Issue 18
  • DOI: 10.1021/jp4011586

Influence of Force Fields and Quantum Chemistry Approach on Spectral Densities of BChl a in Solution and in FMO Proteins
journal, July 2015

  • Chandrasekaran, Suryanarayanan; Aghtar, Mortaza; Valleau, Stéphanie
  • The Journal of Physical Chemistry B, Vol. 119, Issue 31
  • DOI: 10.1021/acs.jpcb.5b03654

Exciton Dissociation at Thiophene/Fullerene Interfaces: The Electronic Structures and Quantum Dynamics
journal, April 2011

  • Tamura, Hiroyuki; Burghardt, Irene; Tsukada, Masaru
  • The Journal of Physical Chemistry C, Vol. 115, Issue 20
  • DOI: 10.1021/jp203174e

Applicability of the Caldeira–Leggett Model to Vibrational Spectroscopy in Solution
journal, June 2015

  • Gottwald, Fabian; Ivanov, Sergei D.; Kühn, Oliver
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 14
  • DOI: 10.1021/acs.jpclett.5b00718

Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H + with D 2
journal, July 1971

  • Tully, John C.; Preston, Richard K.
  • The Journal of Chemical Physics, Vol. 55, Issue 2
  • DOI: 10.1063/1.1675788

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

Communication: Standard surface hopping predicts incorrect scaling for Marcus’ golden-rule rate: The decoherence problem cannot be ignored
journal, November 2011

  • Landry, Brian R.; Subotnik, Joseph E.
  • The Journal of Chemical Physics, Vol. 135, Issue 19
  • DOI: 10.1063/1.3663870

Nonadiabatic molecular dynamics: Validation of the multiple spawning method for a multidimensional problem
journal, May 1998

  • Ben-Nun, M.; Martı́nez, Todd J.
  • The Journal of Chemical Physics, Vol. 108, Issue 17
  • DOI: 10.1063/1.476142

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

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

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

Communication: Nonadiabatic ring-polymer molecular dynamics
journal, July 2013

  • Richardson, Jeremy O.; Thoss, Michael
  • The Journal of Chemical Physics, Vol. 139, Issue 3
  • DOI: 10.1063/1.4816124

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

Mixed quantum-classical dynamics
journal, May 1999

  • Kapral, Raymond; Ciccotti, Giovanni
  • The Journal of Chemical Physics, Vol. 110, Issue 18
  • DOI: 10.1063/1.478811

Classical S Matrix: Numerical Application to Inelastic Collisions
journal, November 1970

  • Miller, William H.
  • The Journal of Chemical Physics, Vol. 53, Issue 9
  • DOI: 10.1063/1.1674535

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

A relationship between semiclassical and centroid correlation functions
journal, May 2003

  • Shi, Qiang; Geva, Eitan
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564814

Practical evaluation of condensed phase quantum correlation functions: A Feynman–Kleinert variational linearized path integral method
journal, December 2003

  • Poulsen, Jens Aage; Nyman, Gunnar; Rossky, Peter J.
  • The Journal of Chemical Physics, Vol. 119, Issue 23
  • DOI: 10.1063/1.1626631

LAND-map, a linearized approach to nonadiabatic dynamics using the mapping formalism
journal, May 2005

  • Bonella, S.; Coker, D. F.
  • The Journal of Chemical Physics, Vol. 122, Issue 19
  • DOI: 10.1063/1.1896948

Quantum-classical Liouville dynamics in the mapping basis
journal, August 2008

  • Kim, Hyojoon; Nassimi, Ali; Kapral, Raymond
  • The Journal of Chemical Physics, Vol. 129, Issue 8
  • DOI: 10.1063/1.2971041

Communication: Partial linearized density matrix dynamics for dissipative, non-adiabatic quantum evolution
journal, November 2011

  • Huo, Pengfei; Coker, David F.
  • The Journal of Chemical Physics, Vol. 135, Issue 20
  • DOI: 10.1063/1.3664763

Nonadiabatic dynamics in open quantum-classical systems: Forward-backward trajectory solution
journal, December 2012

  • Hsieh, Chang-Yu; Kapral, Raymond
  • The Journal of Chemical Physics, Vol. 137, Issue 22
  • DOI: 10.1063/1.4736841

Ensemble Method in the Theory of Irreversibility
journal, November 1960

  • Zwanzig, Robert
  • The Journal of Chemical Physics, Vol. 33, Issue 5
  • DOI: 10.1063/1.1731409

A new approach to calculating the memory kernel of the generalized quantum master equation for an arbitrary system–bath coupling
journal, December 2003

  • Shi, Qiang; Geva, Eitan
  • The Journal of Chemical Physics, Vol. 119, Issue 23
  • DOI: 10.1063/1.1624830

A semiclassical generalized quantum master equation for an arbitrary system-bath coupling
journal, June 2004

  • Shi, Qiang; Geva, Eitan
  • The Journal of Chemical Physics, Vol. 120, Issue 22
  • DOI: 10.1063/1.1738109

Reduced density matrix hybrid approach: An efficient and accurate method for adiabatic and non-adiabatic quantum dynamics
journal, January 2012

  • Berkelbach, Timothy C.; Reichman, David R.; Markland, Thomas E.
  • The Journal of Chemical Physics, Vol. 136, Issue 3
  • DOI: 10.1063/1.3671372

Reduced density matrix hybrid approach: Application to electronic energy transfer
journal, February 2012

  • Berkelbach, Timothy C.; Markland, Thomas E.; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 136, Issue 8
  • DOI: 10.1063/1.3687342

Efficient and accurate surface hopping for long time nonadiabatic quantum dynamics
journal, July 2013

  • Kelly, Aaron; Markland, Thomas E.
  • The Journal of Chemical Physics, Vol. 139, Issue 1
  • DOI: 10.1063/1.4812355

Accurate nonadiabatic quantum dynamics on the cheap: Making the most of mean field theory with master equations
journal, March 2015

  • Kelly, Aaron; Brackbill, Nora; Markland, Thomas E.
  • The Journal of Chemical Physics, Vol. 142, Issue 9
  • DOI: 10.1063/1.4913686

A variational solution of the time-dependent Schrodinger equation
journal, January 1964

Nonadiabatic dynamics of electron transfer in solution: Explicit and implicit solvent treatments that include multiple relaxation time scales
journal, January 2014

  • Schwerdtfeger, Christine A.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon
  • The Journal of Chemical Physics, Vol. 140, Issue 3
  • DOI: 10.1063/1.4855295

Nonequilibrium quantum dynamics in the condensed phase via the generalized quantum master equation
journal, July 2006

  • Zhang, Ming-Liang; Ka, Being J.; Geva, Eitan
  • The Journal of Chemical Physics, Vol. 125, Issue 4
  • DOI: 10.1063/1.2218342

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

Chemical and Electrochemical Electron-Transfer Theory
journal, October 1964

Systematic convergence in the dynamical hybrid approach for complex systems: A numerically exact methodology
journal, August 2001

  • Wang, Haobin; Thoss, Michael; Miller, William H.
  • The Journal of Chemical Physics, Vol. 115, Issue 7
  • DOI: 10.1063/1.1385561

On the Interpretation of Quantum Coherent Beats Observed in Two-Dimensional Electronic Spectra of Photosynthetic Light Harvesting Complexes
journal, May 2011

  • Ishizaki, Akihito; Fleming, Graham R.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 19
  • DOI: 10.1021/jp112406h

Decoherence reduces thermal energy loss in graphene quantum dots
journal, August 2013

  • Jaeger, H. M.; Green, J. R.; Prezhdo, O. V.
  • Applied Physics Letters, Vol. 103, Issue 7
  • DOI: 10.1063/1.4817269

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Comparison of simple potential functions for simulating liquid water
journal, July 1983

  • Jorgensen, William L.; Chandrasekhar, Jayaraman; Madura, Jeffry D.
  • The Journal of Chemical Physics, Vol. 79, Issue 2
  • DOI: 10.1063/1.445869

Canonical sampling through velocity rescaling
journal, January 2007

  • Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2408420

Electron transfer rates for asymmetric reactions
journal, January 2004

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    [ × clear filter / sort ]

    Works referencing / citing this record:

    Approximate but accurate quantum dynamics from the Mori formalism. II. Equilibrium time correlation functions
    journal, February 2017

    • Montoya-Castillo, Andrés; Reichman, David R.
    • The Journal of Chemical Physics, Vol. 146, Issue 8
    • DOI: 10.1063/1.4975388

    Theoretical-computational modeling of charge transfer and intersystem crossing reactions in complex chemical systems
    journal, January 2018

    • Amadei, Andrea; Aschi, Massimiliano
    • RSC Advances, Vol. 8, Issue 49
    • DOI: 10.1039/c8ra03900c

    Mean field theory of thermal energy transport in molecular junctions
    journal, May 2019

    • Kelly, Aaron
    • The Journal of Chemical Physics, Vol. 150, Issue 20
    • DOI: 10.1063/1.5089885

    Efficient construction of generalized master equation memory kernels for multi-state systems from nonadiabatic quantum-classical dynamics
    journal, June 2019

    • Pfalzgraff, William C.; Montoya-Castillo, Andrés; Kelly, Aaron
    • The Journal of Chemical Physics, Vol. 150, Issue 24
    • DOI: 10.1063/1.5095715

    Condensed phase electron transfer beyond the Condon approximation
    journal, December 2016

    • Mavros, Michael G.; Hait, Diptarka; Van Voorhis, Troy
    • The Journal of Chemical Physics, Vol. 145, Issue 21
    • DOI: 10.1063/1.4971166

    State dependent ring polymer molecular dynamics for investigating excited nonadiabatic dynamics
    journal, June 2019

    • Chowdhury, Sutirtha N.; Huo, Pengfei
    • The Journal of Chemical Physics, Vol. 150, Issue 24
    • DOI: 10.1063/1.5096276

    Generalized quantum master equations in and out of equilibrium: When can one win?
    journal, May 2016

    • Kelly, Aaron; Montoya-Castillo, Andrés; Wang, Lu
    • The Journal of Chemical Physics, Vol. 144, Issue 18
    • DOI: 10.1063/1.4948612

    Nonadiabatic dynamics of electrons and atoms under nonequilibrium conditions
    journal, July 2018

    Approximate but accurate quantum dynamics from the Mori formalism: I. Nonequilibrium dynamics
    journal, May 2016

    • Montoya-Castillo, Andrés; Reichman, David R.
    • The Journal of Chemical Physics, Vol. 144, Issue 18
    • DOI: 10.1063/1.4948408

    Different flavors of nonadiabatic molecular dynamics
    journal, April 2019

    • Agostini, Federica; Curchod, Basile F. E.
    • Wiley Interdisciplinary Reviews: Computational Molecular Science
    • DOI: 10.1002/wcms.1417

    Coupled forward-backward trajectory approach for nonequilibrium electron-ion dynamics
    journal, April 2018

    Coupled forward-backward trajectory approach for non-equilibrium electron-ion dynamics
    text, January 2017

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