Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo

White, Alexander J.; Gorshkov, Vyacheslav N.; Tretiak, Sergei; Mozyrsky, Dmitry

doi:10.1063/1.4923473

Title: Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo

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Abstract

Non-adiabatic dynamics, where systems non-radiatively transition between electronic states, plays a crucial role in many photo-physical processes, such as fluorescence, phosphorescence, and photoisomerization. Methods for the simulation of non-adiabatic dynamics are typically either numerically impractical, highly complex, or based on approximations which can result in failure for even simple systems. Recently, the Semiclassical Monte Carlo (SCMC) approach was developed in an attempt to combine the accuracy of rigorous semiclassical methods with the efficiency and simplicity of widely used surface hopping methods. However, while SCMC was found to be more efficient than other semiclassical methods, it is not yet as efficient as is needed to be used for large molecular systems. Here, we have developed two new methods: the accelerated-SCMC and the accelerated-SCMC with re-Gaussianization, which reduce the cost of the SCMC algorithm up to two orders of magnitude for certain systems. In most cases shown here, the new procedures are nearly as efficient as the commonly used surface hopping schemes, with little to no loss of accuracy. This implies that these modified SCMC algorithms will be of practical numerical solutions for simulating non-adiabatic dynamics in realistic molecular systems.

Authors:

^[1]; Gorshkov, Vyacheslav N. ^[2]; Tretiak, Sergei ^[1]; Mozyrsky, Dmitry ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
National Technical University of Ukraine, Kiev (Ukraine)

Publication Date:: Tue Jul 07 00:00:00 EDT 2015

Research Org.:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1224061

Alternate Identifier(s):: OSTI ID: 1420583

Report Number(s):: LA-UR-15-22765
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US1600411

Grant/Contract Number:: AC52-06NA25396

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 143; Journal Issue: 1; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; surface dynamics; non adiabatic couplings; non adiabatic reactions; molecular dynamics; wave functions

Citation Formats


                    White, Alexander J., Gorshkov, Vyacheslav N., Tretiak, Sergei, and Mozyrsky, Dmitry. Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo.  United States: N. p., 2015. 
Web.  doi:10.1063/1.4923473.

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                    White, Alexander J., Gorshkov, Vyacheslav N., Tretiak, Sergei, & Mozyrsky, Dmitry. Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo.  United States.  https://doi.org/10.1063/1.4923473

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                    White, Alexander J., Gorshkov, Vyacheslav N., Tretiak, Sergei, and Mozyrsky, Dmitry. Tue .  
"Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo".  United States.  https://doi.org/10.1063/1.4923473.  https://www.osti.gov/servlets/purl/1224061.

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@article{osti_1224061,

  title        = {Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo},

  author       = {White, Alexander J. and Gorshkov, Vyacheslav N. and Tretiak, Sergei and Mozyrsky, Dmitry},

  abstractNote = {Non-adiabatic dynamics, where systems non-radiatively transition between electronic states, plays a crucial role in many photo-physical processes, such as fluorescence, phosphorescence, and photoisomerization. Methods for the simulation of non-adiabatic dynamics are typically either numerically impractical, highly complex, or based on approximations which can result in failure for even simple systems. Recently, the Semiclassical Monte Carlo (SCMC) approach was developed in an attempt to combine the accuracy of rigorous semiclassical methods with the efficiency and simplicity of widely used surface hopping methods. However, while SCMC was found to be more efficient than other semiclassical methods, it is not yet as efficient as is needed to be used for large molecular systems. Here, we have developed two new methods: the accelerated-SCMC and the accelerated-SCMC with re-Gaussianization, which reduce the cost of the SCMC algorithm up to two orders of magnitude for certain systems. In most cases shown here, the new procedures are nearly as efficient as the commonly used surface hopping schemes, with little to no loss of accuracy. This implies that these modified SCMC algorithms will be of practical numerical solutions for simulating non-adiabatic dynamics in realistic molecular systems.},

  doi          = {10.1063/1.4923473},

  journal      = {Journal of Chemical Physics},

  number       = 1,

  volume       = 143,

  place        = {United States},

  year         = {Tue Jul 07 00:00:00 EDT 2015},

  month        = {Tue Jul 07 00:00:00 EDT 2015}

}

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