Accurate Spin–Orbit Coupling by Relativistic Mixed-Reference Spin-Flip-TDDFTClick to copy article linkArticle link copied!
- Konstantin KomarovKonstantin KomarovCenter for Quantum Dynamics, Pohang University of Science and Technology, Pohang37673, South KoreaMore by Konstantin Komarov
- Woojin ParkWoojin ParkDepartment of Chemistry, Kyungpook National University, Daegu41566, South KoreaMore by Woojin Park
- Seunghoon Lee*Seunghoon Lee*Email: [email protected]Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California91125, USAMore by Seunghoon Lee
- Tao Zeng*Tao Zeng*Email: [email protected]Department of Chemistry, York University, Toronto, ONM3J 1P3, CanadaMore by Tao Zeng
- Cheol Ho Choi*Cheol Ho Choi*Email: [email protected]Department of Chemistry, Kyungpook National University, Daegu41566, South KoreaMore by Cheol Ho Choi
Abstract
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.
Cited By
This article is cited by 6 publications.
- 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
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, 9526-9537. https://doi.org/10.1021/acs.jpca.4c04521
- 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.
- 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
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, 9518-9524. https://doi.org/10.1021/acs.jpclett.4c02227
- 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
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, 5679-5694. https://doi.org/10.1021/acs.jctc.4c00640
- 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
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, 7671-7684. https://doi.org/10.1021/acs.jctc.3c00884
- 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
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, 8896-8908. https://doi.org/10.1021/acs.jpclett.3c02296
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