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Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) as a Simple yet Accurate Method for Diradicals and Diradicaloids

Horbatenko, Yevhen and Sadiq, Saima and Lee, Seunghoon and Filatov, Michael and Choi, Cheol Ho (2021) Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) as a Simple yet Accurate Method for Diradicals and Diradicaloids. Journal of Chemical Theory and Computation, 17 (2). pp. 848-859. ISSN 1549-9618. https://resolver.caltech.edu/CaltechAUTHORS:20210112-091401215

[img] PDF (Adiabatic ST gaps and MAE calculated with both MRSF- and SF-TDDFT (Table S1); comparison of the most important distances in the set of the molecules studied in this work (Figure S1); MO and main electronic configurations of the 1B2 conformation of TMM...) - Supplemental Material
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Abstract

Due to their multiconfigurational nature featuring strong electron correlation, accurate description of diradicals and diradicaloids is a challenge for quantum chemical methods. The recently developed mixed-reference spin-flip (MRSF)-TDDFT method is capable of describing the multiconfigurational electronic states of these systems while avoiding the spin-contamination pitfalls of SF-TDDFT. Here, we apply MRSF-TDDFT to study the adiabatic singlet–triplet (ST) gaps in a series of well-known diradicals and diradicaloids. On average, MRSF displays a very high prediction accuracy of the adiabatic ST gaps with the mean absolute error (MAE) amounting to 0.14 eV. In addition, MRSF is capable of accurately describing the effect of the Jahn–Teller distortion occurring in the trimethylenemethane diradical, the violation of the Hund rule in a series of the didehydrotoluene diradicals, and the potential energy surfaces of the didehydrobenzene (benzyne) diradicals. A convenient criterion for distinguishing diradicals and diradicaloids is suggested on the basis of the easily obtainable quantities. In all of these cases, which are difficult for the conventional methods of density functional theory (DFT), MRSF shows results consistent with the experiment and the high-level ab initio computations. Hence, the present study documents the reliability and accuracy of MRSF and lays out the guidelines for its application to strongly correlated molecular systems.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jctc.0c01074DOIArticle
ORCID:
AuthorORCID
Horbatenko, Yevhen0000-0002-6913-9241
Lee, Seunghoon0000-0003-3665-587X
Filatov, Michael0000-0002-1541-739X
Choi, Cheol Ho0000-0002-8757-1396
Additional Information:© 2021 American Chemical Society. Received: October 12, 2020; Published: January 5, 2021. This work has supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT)(No.2020R1A2C2008246). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Research Foundation of Korea2020R1A2C2008246
Subject Keywords:Contamination, Quantum mechanics, Mathematical methods, Potential energy, Molecules
Issue or Number:2
Record Number:CaltechAUTHORS:20210112-091401215
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210112-091401215
Official Citation:Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) as a Simple yet Accurate Method for Diradicals and Diradicaloids. Yevhen Horbatenko, Saima Sadiq, Seunghoon Lee, Michael Filatov, and Cheol Ho Choi. Journal of Chemical Theory and Computation 2021 17 (2), 848-859; DOI: 10.1021/acs.jctc.0c01074
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107415
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jan 2021 17:54
Last Modified:10 Feb 2021 20:34

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