ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

From Surface Hopping to Quantum Dynamics and Back. Finding Essential Electronic and Nuclear Degrees of Freedom and Optimal Surface Hopping Parameters

  • Sandra Gómez
    Sandra Gómez
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, 1010 Vienna, Austria
  • Moritz Heindl
    Moritz Heindl
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, 1010 Vienna, Austria
  • András Szabadi
    András Szabadi
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, 1010 Vienna, Austria
  • , and 
  • Leticia González*
    Leticia González
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, 1010 Vienna, Austria
    *E-mail: [email protected]
Cite this: J. Phys. Chem. A 2019, 123, 38, 8321–8332
Publication Date (Web):September 3, 2019
https://doi.org/10.1021/acs.jpca.9b06103
Copyright © 2019 American Chemical Society

    Article Views

    884

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    We report an efficient iterative procedure that exploits surface-hopping trajectory methods and quantum dynamics to achieve two complementary purposes: to identify the minimum dimensionality of a molecular Hamiltonian in terms of electronic and nuclear degrees of freedom to study radiationless relaxation mechanisms as well as to provide a reference quantum dynamical calculation that allows assessing of the validity of surface-hopping parameters. This double goal is achieved by a feedback loop between surface hopping and MCTDH calculations based on potential energy surfaces parametrized with a linear vibronic coupling method. Initially, a surface hopping calculation in full dimensionality with a chosen set of parameters is performed, and it is repeated, gradually reducing its dimensionality until divergence with the initial calculation is observed or the system is small enough to be treated quantum dynamically. A comparison between the quantum dynamics and surface hopping simulations dictates the validity of the surface hopping parameters. Using these new parameters, the reduction loop is started again, until convergence. As an example, this strategy is applied to simulate the ultrafast intersystem crossing dynamics of [PtBr6]2– in solution. The 15-dimensional space initially including 200 electronic states is reduced to a 9-dimensional problem with 76 electronic states, without a considerable loss of accuracy.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.9b06103.

    • LVC parametrization data, normal mode gif, and MCTDH data necessary to reproduce the results (ZIP)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 25 publications.

    1. Thierry Tran, Anthony Ferté, Morgane Vacher. Simulating Attochemistry: Which Dynamics Method to Use?. The Journal of Physical Chemistry Letters 2024, 15 (13) , 3646-3652. https://doi.org/10.1021/acs.jpclett.4c00106
    2. Adam Šrut, Vera Krewald. Vibrational Coherences of the Photoinduced Mixed-Valent Creutz–Taube Ion Revealed by Excited State Dynamics. The Journal of Physical Chemistry A 2023, 127 (47) , 9911-9920. https://doi.org/10.1021/acs.jpca.3c04415
    3. Hassiel Negrin-Yuvero, Victor Manuel Freixas, Dianelys Ondarse-Alvarez, Laura Alfonso-Hernandez, German Rojas-Lorenzo, Adolfo Bastida, Sergei Tretiak, Sebastian Fernandez-Alberti. Vibrational Funnels for Energy Transfer in Organic Chromophores. The Journal of Physical Chemistry Letters 2023, 14 (20) , 4673-4681. https://doi.org/10.1021/acs.jpclett.3c00748
    4. Hassiel Negrin-Yuvero, Aliya Mukazhanova, Victor M. Freixas, Sergei Tretiak, Sahar Sharifzadeh, Sebastian Fernandez-Alberti. Vibronic Photoexcitation Dynamics of Perylene Diimide: Computational Insights. The Journal of Physical Chemistry A 2022, 126 (5) , 733-741. https://doi.org/10.1021/acs.jpca.1c09484
    5. J. Patrick Zobel, Moritz Heindl, Felix Plasser, Sebastian Mai, Leticia González. Surface Hopping Dynamics on Vibronic Coupling Models. Accounts of Chemical Research 2021, 54 (20) , 3760-3771. https://doi.org/10.1021/acs.accounts.1c00485
    6. Mátyás Pápai. Photoinduced Low-Spin → High-Spin Mechanism of an Octahedral Fe(II) Complex Revealed by Synergistic Spin-Vibronic Dynamics. Inorganic Chemistry 2021, 60 (18) , 13950-13954. https://doi.org/10.1021/acs.inorgchem.1c01838
    7. Julia Westermayr, Philipp Marquetand. Machine Learning for Electronically Excited States of Molecules. Chemical Reviews 2021, 121 (16) , 9873-9926. https://doi.org/10.1021/acs.chemrev.0c00749
    8. J. Patrick Zobel, Leticia González. The Quest to Simulate Excited-State Dynamics of Transition Metal Complexes. JACS Au 2021, 1 (8) , 1116-1140. https://doi.org/10.1021/jacsau.1c00252
    9. H. Negrin-Yuvero, V. M. Freixas, B. Rodriguez-Hernandez, G. Rojas-Lorenzo, S. Tretiak, A. Bastida, S. Fernandez-Alberti. Photoinduced Dynamics with Constrained Vibrational Motion: FrozeNM Algorithm. Journal of Chemical Theory and Computation 2020, 16 (12) , 7289-7298. https://doi.org/10.1021/acs.jctc.0c00930
    10. Yinan Shu, Linyao Zhang, Sebastian Mai, Shaozeng Sun, Leticia González, Donald G. Truhlar. Implementation of Coherent Switching with Decay of Mixing into the SHARC Program. Journal of Chemical Theory and Computation 2020, 16 (6) , 3464-3475. https://doi.org/10.1021/acs.jctc.0c00112
    11. Vjacheslav P. Grivin, Svetlana G. Matveeva, Roman G. Fedunov, Vadim V. Yanshole, Danila B. Vasilchenko, Evgeni M. Glebov. Photochemistry of (n-Bu4N)2[Pt(NO3)6] in acetonitrile. Photochemical & Photobiological Sciences 2024, 23 (4) , 747-755. https://doi.org/10.1007/s43630-024-00550-5
    12. Joachim Galiana, Benjamin Lasorne. Excitation energy transfer and vibronic relaxation through light-harvesting dendrimer building blocks: A nonadiabatic perspective. The Journal of Chemical Physics 2024, 160 (10) https://doi.org/10.1063/5.0193264
    13. Alberto Martín Santa Daría, Lola González-Sánchez, Sandra Gómez. Coronene: a model for ultrafast dynamics in graphene nanoflakes and PAHs. Physical Chemistry Chemical Physics 2024, 63 https://doi.org/10.1039/D3CP03656A
    14. Olga S. Bokareva, Oliver Kühn. Quantum Dynamics of Photoactive Transition Metal Complexes. A Case Study of Model Reduction. 2024, 385-393. https://doi.org/10.1016/B978-0-12-821978-2.00142-2
    15. Pijush Karak, Torsha Moitra, Swapan Chakrabarti. Relativistic Effects on Photodynamical Processes. 2024, 258-279. https://doi.org/10.1016/B978-0-12-821978-2.00100-8
    16. Thomas J Penfold, Julien Eng. Mind the GAP: quantifying the breakdown of the linear vibronic coupling Hamiltonian. Physical Chemistry Chemical Physics 2023, 25 (10) , 7195-7204. https://doi.org/10.1039/D2CP05576G
    17. Shiladitya Karmakar, Pradip Chakraborty, Tanusri Saha-Dasgupta. Trend in light-induced excited-state spin trapping in Fe( ii )-based spin crossover systems. Physical Chemistry Chemical Physics 2022, 24 (17) , 10201-10209. https://doi.org/10.1039/D2CP00539E
    18. E. M. Glebov. Femtochemistry methods for studying the photophysics and photochemistry of halide complexes of platinum metals. Russian Chemical Bulletin 2022, 71 (5) , 858-877. https://doi.org/10.1007/s11172-022-3486-2
    19. Moritz Heindl, Leticia González. Validating fewest-switches surface hopping in the presence of laser fields. The Journal of Chemical Physics 2021, 154 (14) https://doi.org/10.1063/5.0044807
    20. Jiawei Peng, Yu Xie, Deping Hu, Zhenggang Lan. Analysis of bath motion in MM-SQC dynamics via dimensionality reduction approach: Principal component analysis. The Journal of Chemical Physics 2021, 154 (9) https://doi.org/10.1063/5.0039743
    21. Torsha Moitra, Pijush Karak, Sayantani Chakraborty, Kenneth Ruud, Swapan Chakrabarti. Behind the scenes of spin-forbidden decay pathways in transition metal complexes. Physical Chemistry Chemical Physics 2021, 23 (1) , 59-81. https://doi.org/10.1039/D0CP05108J
    22. Julia Westermayr, Philipp Marquetand. Machine learning and excited-state molecular dynamics. Machine Learning: Science and Technology 2020, 1 (4) , 043001. https://doi.org/10.1088/2632-2153/ab9c3e
    23. Julia Westermayr, Philipp Marquetand. Machine Learning for Nonadiabatic Molecular Dynamics. 2020, 76-108. https://doi.org/10.1039/9781839160233-00076
    24. Thierry Tran, Andrew J. Jenkins, Graham A. Worth, Michael A. Robb. The quantum-Ehrenfest method with the inclusion of an IR pulse: Application to electron dynamics of the allene radical cation. The Journal of Chemical Physics 2020, 153 (3) https://doi.org/10.1063/5.0015937
    25. Alexey A. Melnikov, Ivan P. Pozdnyakov, Sergey V. Chekalin, Evgeni M. Glebov. Direct measurement of ultrafast intersystem crossing time for the PtIVBr62− complex. Mendeleev Communications 2020, 30 (4) , 509-511. https://doi.org/10.1016/j.mencom.2020.07.036

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect