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Title: Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence

Abstract

Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety of frameworks, ranging from fully quantum treatment of nuclei to semiclassical and mixed quantum–classical approaches, were developed. These algorithms are then coupled to specific electronic structure techniques. Such diversity and lack of standardized implementation make it difficult to compare the performance of different methodologies when treating realistic systems. Here, we compare three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). These approaches are implemented in the NEXMD software, which features a common computational chemistry model. The resulting comparisons reveal the method performance for population relaxation and coherent vibronic dynamics. Finally, we study the numerical convergence of MCE-AIMC algorithms by considering the number of trajectories, cloning thresholds, and Gaussian wavepacket width. Our results provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [3];  [4];  [1]; ORCiD logo [2]
  1. Universidad Nacional de Quilmes, Bernal (Argentina)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Leeds (United Kingdom); Bristol Univ. (United Kingdom)
  4. Univ. of Leeds (United Kingdom)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1841929
Report Number(s):
LA-UR-21-20549
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 12; Journal Issue: 11; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Freixas, Victor M., White, Alexander James, Nelson, Tammie Renee, Song, Huajing, Makhov, Dmitry V., Shalashilin, Dmitrii, Fernandez-Alberti, S., and Tretiak, Sergei. Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence. United States: N. p., 2021. Web. doi:10.1021/acs.jpclett.1c00266.
Freixas, Victor M., White, Alexander James, Nelson, Tammie Renee, Song, Huajing, Makhov, Dmitry V., Shalashilin, Dmitrii, Fernandez-Alberti, S., & Tretiak, Sergei. Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence. United States. https://doi.org/10.1021/acs.jpclett.1c00266
Freixas, Victor M., White, Alexander James, Nelson, Tammie Renee, Song, Huajing, Makhov, Dmitry V., Shalashilin, Dmitrii, Fernandez-Alberti, S., and Tretiak, Sergei. Wed . "Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence". United States. https://doi.org/10.1021/acs.jpclett.1c00266. https://www.osti.gov/servlets/purl/1841929.
@article{osti_1841929,
title = {Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence},
author = {Freixas, Victor M. and White, Alexander James and Nelson, Tammie Renee and Song, Huajing and Makhov, Dmitry V. and Shalashilin, Dmitrii and Fernandez-Alberti, S. and Tretiak, Sergei},
abstractNote = {Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety of frameworks, ranging from fully quantum treatment of nuclei to semiclassical and mixed quantum–classical approaches, were developed. These algorithms are then coupled to specific electronic structure techniques. Such diversity and lack of standardized implementation make it difficult to compare the performance of different methodologies when treating realistic systems. Here, we compare three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). These approaches are implemented in the NEXMD software, which features a common computational chemistry model. The resulting comparisons reveal the method performance for population relaxation and coherent vibronic dynamics. Finally, we study the numerical convergence of MCE-AIMC algorithms by considering the number of trajectories, cloning thresholds, and Gaussian wavepacket width. Our results provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.},
doi = {10.1021/acs.jpclett.1c00266},
journal = {Journal of Physical Chemistry Letters},
number = 11,
volume = 12,
place = {United States},
year = {Wed Mar 17 00:00:00 EDT 2021},
month = {Wed Mar 17 00:00:00 EDT 2021}
}

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