Freixas, VM, White, AJ, Nelson, T et al. (5 more authors) (2021) Nonadiabatic Excited-State Molecular Dynamics Methodologies: Comparison and Convergence. Journal of Physical Chemistry Letters, 12 (11). pp. 2970-2982. ISSN 1948-7185
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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2021 American Chemical Society. This is an author produced version of an article published in Journal of Physical Chemistry Letters. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 16 Mar 2021 16:07 |
Last Modified: | 17 Mar 2022 01:38 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpclett.1c00266 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:172025 |