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How Beneficial Is the Explicit Account of Doubly-Excited Configurations in Linear Response Theory?

Horbatenko, Yevhen and Lee, Seunghoon and Filatov, Michael and Choi, Cheol Ho (2021) How Beneficial Is the Explicit Account of Doubly-Excited Configurations in Linear Response Theory? Journal of Chemical Theory and Computation, 17 (2). pp. 975-984. ISSN 1549-9618.

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In different branches of time-dependent density functional theory (TDDFT), the static and dynamic electron correlation enters in different ways. The standard spin-conserving linear response (LR-TDDFT) methodology includes explicitly the contributions of the singly-excited configurations; however, it relies on an implicit account of the electron correlation through an (approximate) exchange-correlation (XC) functional. In the mixed-reference spin-flip TDDFT (MRSF-TDDFT), a number of doubly-excited (DE) configurations are explicitly included in the description of their response states. Here, the importance of the explicit account of DE is investigated for the lowest four excited singlet states of all-trans-polyenes up to C₂₄H₂₆. For the optically bright 1B_u⁺ state, the DE contribution in MRSF-TDDFT approaches 10% with the increasing system size. For the optically dark 2Ag⁻ state, the DE contribution increases from ca. 13% (C₄H₆) to nearly 30% (C₂₄H₂₆). An even more considerable DE contribution (∼50%) is observed in the higher 1B_u⁻ states. As LR-TDDFT misses these contributions entirely, its ability to accurately describe the excited states is limited by the XC functional. The hybrid XC functionals with a small fraction of the exact exchange, e.g., B3LYP, may mimic certain effects of DE through the self-interaction error (SIE). However, the description of the 1B_u⁺ state by LR-TDDFT remains poor. On the other hand, MRSF-TDDFT can flexibly take an implicit (through the XC functional) and an explicit (through DE) account of the electron correlation, which enables a more balanced description of various types of the excited states regardless of their character, thus reducing the chances of failure.

Item Type:Article
Related URLs:
URLURL TypeDescription
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: November 21, 2020; Published: January 4, 2021. This work was supported by the Samsung Science and Technology Foundations (SSTF-BA1701-12). Author Contributions. Y.H. and S.L. contributed equally to this work. The authors declare no competing financial interest.
Funding AgencyGrant Number
Samsung Science and Technology FoundationSSTF-BA1701-12
Subject Keywords:Time dependant density functional theory, Energy, Mathematical methods, Electron correlation, Excited states
Issue or Number:2
Record Number:CaltechAUTHORS:20210112-091401023
Persistent URL:
Official Citation:How Beneficial Is the Explicit Account of Doubly-Excited Configurations in Linear Response Theory? Yevhen Horbatenko, Seunghoon Lee, Michael Filatov, and Cheol Ho Choi. Journal of Chemical Theory and Computation 2021 17 (2), 975-984; DOI: 10.1021/acs.jctc.0c01214
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107414
Deposited By: George Porter
Deposited On:12 Jan 2021 18:19
Last Modified:09 Feb 2021 17:05

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