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Scalable Ehrenfest Molecular Dynamics Exploiting the Locality of Density-Functional Tight-Binding Hamiltonian
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    Scalable Ehrenfest Molecular Dynamics Exploiting the Locality of Density-Functional Tight-Binding Hamiltonian
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    • Hiroki Uratani
      Hiroki Uratani
      Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
    • Hiromi Nakai*
      Hiromi Nakai
      Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
      Waseda Research Institute for Science and Engineering (WISE), 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
      Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8245, Japan
      *Email: [email protected]
      More by Hiromi Nakai
    Other Access OptionsSupporting Information (1)

    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2021, 17, 12, 7384–7396
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    https://doi.org/10.1021/acs.jctc.1c00950
    Published December 3, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    To explore the science behind excited-state dynamics in high-complexity chemical systems, a scalable nonadiabatic molecular dynamics (MD) technique is indispensable. In this study, by treating the electronic degrees of freedom at the density-functional tight-binding level, we developed and implemented a reduced scaling and multinode-parallelizable Ehrenfest MD method. To achieve this goal, we introduced a concept called patchwork approximation (PA), where the effective Hamiltonian for real-time propagation of the electronic density matrix is partitioned into a set of local parts. Numerical results for giant icosahedral fullerenes, which comprise up to 6000 atoms, suggest that the scaling of the present PA-based method is less than quadratic, which yields a significant advantage over the conventional cubic scaling method in terms of computational time. The acceleration by the parallelization on multiple nodes was also assessed. Furthermore, the electronic and structural dynamics resulting from the perturbation by the external electric field were accurately reproduced with the PA, even when the electronic excitation was spatially delocalized.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jctc.1c00950.

    • Atomic coordinates of (1,1)–(10,10) and the geometry-optimized (4,4) fullerenes in the XYZ format (ZIP)

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    Cited By

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    This article is cited by 5 publications.

    1. Gonzalo Díaz Mirón, Carlos R. Lien-Medrano, Debarshi Banerjee, Uriel N. Morzan, Michael A. Sentef, Ralph Gebauer, Ali Hassanali. Exploring the Mechanisms behind Non-aromatic Fluorescence with the Density Functional Tight Binding Method. Journal of Chemical Theory and Computation 2024, 20 (9) , 3864-3878. https://doi.org/10.1021/acs.jctc.4c00125
    2. Mohammad Shakiba, Alexey V. Akimov. Dependence of Electron–Hole Recombination Rates on Charge Carrier Concentration: A Case Study of Nonadiabatic Molecular Dynamics in Graphitic Carbon Nitride Monolayers. The Journal of Physical Chemistry C 2023, 127 (19) , 9083-9096. https://doi.org/10.1021/acs.jpcc.3c00211
    3. Hiroki Uratani, Hiromi Nakai. Nanoscale and Real-Time Nuclear–Electronic Dynamics Simulation Study of Charge Transfer at the Donor–Acceptor Interface in Organic Photovoltaics. The Journal of Physical Chemistry Letters 2023, 14 (9) , 2292-2300. https://doi.org/10.1021/acs.jpclett.2c03808
    4. Hiromi Nakai, Masato Kobayashi, Takeshi Yoshikawa, Junji Seino, Yasuhiro Ikabata, Yoshifumi Nishimura. Divide-and-Conquer Linear-Scaling Quantum Chemical Computations. The Journal of Physical Chemistry A 2023, 127 (3) , 589-618. https://doi.org/10.1021/acs.jpca.2c06965
    5. Mohammad Shakiba, Elizabeth Stippell, Wei Li, Alexey V. Akimov. Nonadiabatic Molecular Dynamics with Extended Density Functional Tight-Binding: Application to Nanocrystals and Periodic Solids. Journal of Chemical Theory and Computation 2022, 18 (9) , 5157-5180. https://doi.org/10.1021/acs.jctc.2c00297

    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2021, 17, 12, 7384–7396
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jctc.1c00950
    Published December 3, 2021
    Copyright © 2021 American Chemical Society

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