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Accurate Spin–Orbit Coupling by Relativistic Mixed-Reference Spin-Flip-TDDFT
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    Accurate Spin–Orbit Coupling by Relativistic Mixed-Reference Spin-Flip-TDDFT
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2023, 19, 3, 953–964
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    https://doi.org/10.1021/acs.jctc.2c01036
    Published January 18, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    Relativistic mixed-reference spin-flip (MRSF)-TDDFT is developed considering the spin–orbit coupling (SOC) within the mean-field approximation. The resulting SOC-MRSF faithfully reproduces the experiments with very high accuracy, which is also consistent with the values by four-component (4c) relativistic CASSCF and 4c-CASPT2 in the spin–orbit-energy splitting calculations of the C, Si, and Ge atoms. Even for the fifth-row element Sn, the SOC-MRSF yielded accurate splittings (∼ 3 % error). In the SOC calculations of the molecular 4-thiothymine with a third-row element, SOC-MRSF values are in excellent agreement with those of the SO-GMC-QDPT2 level, regardless of geometries and exchange-correlation functionals. The same SOC-MRSF predicted the anticipated chance of S1 (nπ*) → T1 (ππ*) intersystem crossing, even in thymine with only second-row elements. With its accuracy and practicality, thus, SOC-MRSF is a promising electronic structure protocol in challenging situations such as nonadiabatic molecular dynamics (NAMD) incorporating both internal conversions and intersystem crossings in large systems.

    Copyright © 2023 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.2c01036.

    • The elements of spin-dependent transition density matrix, explicit expressions for non-SOC-MRSF wave functions, as well as one figure and three tables are provided in a separate supplementary material (PDF)

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    Cited By

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    This article is cited by 6 publications.

    1. Konstantin Komarov, Minseok Oh, Hiroya Nakata, Seunghoon Lee, Cheol Ho Choi. UMRSF-TDDFT: Unrestricted Mixed-Reference Spin-Flip-TDDFT. The Journal of Physical Chemistry A 2024, 128 (43) , 9526-9537. https://doi.org/10.1021/acs.jpca.4c04521
    2. Vladimir Mironov, Konstantin Komarov, Jingbai Li, Igor Gerasimov, Hiroya Nakata, Mohsen Mazaherifar, Kazuya Ishimura, Woojin Park, Alireza Lashkaripour, Minseok Oh, Miquel Huix-Rotllant, Seunghoon Lee, Cheol Ho Choi. OpenQP: A Quantum Chemical Platform Featuring MRSF-TDDFT with an Emphasis on Open-Source Ecosystem. Journal of Chemical Theory and Computation 2024, Article ASAP.
    3. Maryam Farmani, Seunghoon Lee, Tao Zeng, Cheol Ho Choi. Chemoexcited Formation and Radiationless Decay Dynamics of Firefly Chromophore. The Journal of Physical Chemistry Letters 2024, 15 (37) , 9518-9524. https://doi.org/10.1021/acs.jpclett.4c02227
    4. Woojin Park, Alireza Lashkaripour, Konstantin Komarov, Seunghoon Lee, Miquel Huix-Rotllant, Cheol Ho Choi. Toward Consistent Predictions of Core/Valence Ionization Potentials and Valence Excitation Energies by MRSF-TDDFT. Journal of Chemical Theory and Computation 2024, 20 (13) , 5679-5694. https://doi.org/10.1021/acs.jctc.4c00640
    5. Konstantin Komarov, Woojin Park, Seunghoon Lee, Miquel Huix-Rotllant, Cheol Ho Choi. Doubly Tuned Exchange–Correlation Functionals for Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory. Journal of Chemical Theory and Computation 2023, 19 (21) , 7671-7684. https://doi.org/10.1021/acs.jctc.3c00884
    6. Woojin Park, Konstantin Komarov, Seunghoon Lee, Cheol Ho Choi. Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory: Multireference Advantages with the Practicality of Linear Response Theory. The Journal of Physical Chemistry Letters 2023, 14 (39) , 8896-8908. https://doi.org/10.1021/acs.jpclett.3c02296

    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2023, 19, 3, 953–964
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jctc.2c01036
    Published January 18, 2023
    Copyright © 2023 American Chemical Society

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