Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation

Cotton, Stephen J.; Miller, William H.

doi:10.1063/1.5094458

Title: Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation

Abstract

An electronic zero-point energy (ZPE) adjustment protocol is proposed within the context of the symmetrical quasiclassical (SQC) quantization of the electronic oscillator degrees of freedom (DOF) in classical Meyer-Miller (MM) vibronic dynamics for the molecular dynamics treatment of electronically nonadiabatic processes. The “adjustment” procedure maintains the same initial and final distributions of coordinates and momenta in the electronic oscillator DOF as previously given by the SQC windowing protocol but modifies the ZPE parameter in the MM Hamiltonian, on a per trajectory basis, so that the initial nuclear forces are precisely those corresponding to the initial electronic quantum state. Examples demonstrate that this slight modification to the standard SQC/MM approach greatly improves treatment of the multistate nonadiabatic dynamics following a Franck-Condon type vertical excitation onto a highly repulsive potential energy surface as is typical in the photodissociation context.

Authors:

^[1];

^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Mon May 20 00:00:00 EDT 2019

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)

OSTI Identifier:: 1577592

Alternate Identifier(s):: OSTI ID: 1514746

Grant/Contract Number:: AC02-05CH11231; CHE-1464647

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 150; Journal Issue: 19; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Quantum chemical dynamics; Molecular dynamics; Zero point energy; Classical trajectory method; Non-adiabatic molecular dynamics; Photodissociation; Quantum algorithms; Quantum effects; Potential energy surfaces

Citation Formats


                    Cotton, Stephen J., and Miller, William H. Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation.  United States: N. p., 2019. 
Web.  doi:10.1063/1.5094458.

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                    Cotton, Stephen J., & Miller, William H. Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation.  United States.  https://doi.org/10.1063/1.5094458

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                    Cotton, Stephen J., and Miller, William H. Mon .  
"Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation".  United States.  https://doi.org/10.1063/1.5094458.  https://www.osti.gov/servlets/purl/1577592.

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@article{osti_1577592,

  title        = {Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation},

  author       = {Cotton, Stephen J. and Miller, William H.},

  abstractNote = {An electronic zero-point energy (ZPE) adjustment protocol is proposed within the context of the symmetrical quasiclassical (SQC) quantization of the electronic oscillator degrees of freedom (DOF) in classical Meyer-Miller (MM) vibronic dynamics for the molecular dynamics treatment of electronically nonadiabatic processes. The “adjustment” procedure maintains the same initial and final distributions of coordinates and momenta in the electronic oscillator DOF as previously given by the SQC windowing protocol but modifies the ZPE parameter in the MM Hamiltonian, on a per trajectory basis, so that the initial nuclear forces are precisely those corresponding to the initial electronic quantum state. Examples demonstrate that this slight modification to the standard SQC/MM approach greatly improves treatment of the multistate nonadiabatic dynamics following a Franck-Condon type vertical excitation onto a highly repulsive potential energy surface as is typical in the photodissociation context.},

  doi          = {10.1063/1.5094458},

  journal      = {Journal of Chemical Physics},

  number       = 19,

  volume       = 150,

  place        = {United States},

  year         = {Mon May 20 00:00:00 EDT 2019},

  month        = {Mon May 20 00:00:00 EDT 2019}

}

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Works referenced in this record:

A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states
journal, March 2019

Cotton, Stephen J.; Miller, William H.
The Journal of Chemical Physics, Vol. 150, Issue 10
DOI: 10.1063/1.5087160

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

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electronically non-adiabatic processes
journal, December 2013

Cotton, Stephen J.; Miller, William H.
The Journal of Chemical Physics, Vol. 139, Issue 23
DOI: 10.1063/1.4845235

Coherence-Controlled Nonadiabatic Dynamics via State-Space Decomposition: A Consistent Way To Incorporate Ehrenfest and Born–Oppenheimer-Like Treatments of Nuclear Motion
journal, October 2016

Tao, Guohua
The Journal of Physical Chemistry Letters, Vol. 7, Issue 21
DOI: 10.1021/acs.jpclett.6b01857

Classical molecular dynamics simulation of electronically non-adiabatic processes
journal, January 2016

Miller, William H.; Cotton, Stephen J.
Faraday Discussions, Vol. 195
DOI: 10.1039/c6fd00181e

Semi-classical path integral non-adiabatic dynamics: a partial linearized classical mapping Hamiltonian approach
journal, May 2012

Huo, Pengfei; Coker, David F.
Molecular Physics, Vol. 110, Issue 9-10
DOI: 10.1080/00268976.2012.684896

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

A new symmetrical quasi-classical model for electronically non-adiabatic processes: Application to the case of weak non-adiabatic coupling
journal, October 2016

Cotton, Stephen J.; Miller, William H.
The Journal of Chemical Physics, Vol. 145, Issue 14
DOI: 10.1063/1.4963914

Ultrafast non-adiabatic dynamics of systems with multiple surface crossings: a test of the Meyer–Miller Hamiltonian with semiclassical initial value representation methods
journal, December 2001

Coronado, Eduardo A.; Xing, Jianhua; Miller, William H.
Chemical Physics Letters, Vol. 349, Issue 5-6
DOI: 10.1016/s0009-2614(01)01242-8

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

Duke, Jessica R.; Ananth, Nandini
The Journal of Physical Chemistry Letters, Vol. 6, Issue 21
DOI: 10.1021/acs.jpclett.5b01957

Communication: Wigner functions in action-angle variables, Bohr-Sommerfeld quantization, the Heisenberg correspondence principle, and a symmetrical quasi-classical approach to the full electronic density matrix
journal, August 2016

Miller, William H.; Cotton, Stephen J.
The Journal of Chemical Physics, Vol. 145, Issue 8
DOI: 10.1063/1.4961551

An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability
journal, April 2016

Bellonzi, Nicole; Jain, Amber; Subotnik, Joseph E.
The Journal of Chemical Physics, Vol. 144, Issue 15
DOI: 10.1063/1.4946810

Works referencing / citing this record:

Initial sampling in symmetrical quasiclassical dynamics based on Li–Miller mapping Hamiltonian
journal, January 2019

Zheng, Jie; Xie, Yu; Jiang, Shengshi
Physical Chemistry Chemical Physics, Vol. 21, Issue 48
DOI: 10.1039/c9cp03975a

Special topic on dynamics of open quantum systems
journal, January 2020

Berkelbach, Timothy C.; Thoss, Michael
The Journal of Chemical Physics, Vol. 152, Issue 2
DOI: 10.1063/1.5142731

Initial Sampling in Symmetrical Quasiclassical Dynamics Based on Li-Miller Mapping Hamiltonian
text, January 2018

Zheng, Jie; Xie, Yu; Jiang, Sheng-shi
arXiv
DOI: 10.48550/arxiv.1811.00257

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Title: Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation

Abstract

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