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Internal Conversion between Bright (1¹Bᵤ⁺) and Dark (2¹Ag⁻) States in s-trans-Butadiene and s-trans-Hexatriene

Park, Woojin and Shen, Jun and Lee, Seunghoon and Piecuch, Piotr and Filatov, Michael and Choi, Cheol Ho (2021) Internal Conversion between Bright (1¹Bᵤ⁺) and Dark (2¹Ag⁻) States in s-trans-Butadiene and s-trans-Hexatriene. Journal of Physical Chemistry Letters, 12 (39). pp. 9720-9729. ISSN 1948-7185. doi:10.1021/acs.jpclett.1c02707. https://resolver.caltech.edu/CaltechAUTHORS:20211008-224623371

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Abstract

Internal conversion (IC) between the two lowest singlet excited states, 1¹B_u⁺ and 2¹A_g⁻, of s-trans-butadiene and s-trans-hexatriene is investigated using a series of single- and multi- reference wave function and density functional theory (DFT) methodologies. Three independent types of the equation-of-motion coupled-cluster (EOMCC) theory capable of providing an accurate and balanced description of one- as well as two-electron transitions, abbreviated as δ-CR-EOMCC(2,3), DIP-EOMCC(4h2p){N₀}, and DEA-EOMCC(4p2h){N_u} or DEA-EOMCC(3p1h,4p2h){N_u}, consistently predict that the 1¹B_u⁺/2¹A_g⁻ crossing in both molecules occurs along the bond length alternation coordinate. However, the analogous 1¹B_u⁺ and 2¹A_g⁻ potentials obtained with some multireference approaches, such as CASSCF and MRCIS(D), as well as with the linear-response formulation of time-dependent DFT (TDDFT), do not cross. Hence, caution needs to be exercised when studying the low-lying singlet excited states of polyenes with conventional multiconfigurational methods and TDDFT. The multistate many-body perturbation theory methods, such as XMCQDPT2, do correctly reproduce the curve crossing. Among the simplest and least expensive computational methodologies, the DFT approaches that incorporate the contributions of doubly excited configurations, abbreviated as MRSF (mixed reference spin-flip) TDDFT and SSR(4,4), accurately reproduce our best EOMCC results. This is highly promising for nonadiabatic molecular dynamics simulations in larger systems.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpclett.1c02707DOIArticle
ORCID:
AuthorORCID
Shen, Jun0000-0003-1838-3719
Lee, Seunghoon0000-0003-3665-587X
Piecuch, Piotr0000-0002-7207-1815
Filatov, Michael0000-0002-1541-739X
Choi, Cheol Ho0000-0002-8757-1396
Alternate Title:Internal Conversion between Bright (11Bu+) and Dark (21Ag–) States in s-trans-Butadiene and s-trans-Hexatriene, Internal Conversion between Bright (1¹B_u⁺) and Dark (2¹A_g⁻) States in s-trans-Butadiene and s-trans-Hexatriene
Additional Information:© 2021 The Authors. Published by American Chemical Society. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) Received 17 August 2021. Accepted 20 September 2021. Published online 30 September 2021. Published in issue 7 October 2021. This work was supported by the Samsung Science and Technology Foundations Grant SSTF-BA1701-12 (to C.H.C.) for fundamental theory developments, the NRF grants 2019H1D3A2A02102948 (to M.F.) and 2020R1A2C2008246 and 2020R1A5A1019141 (to C.H.C.) funded by the Ministry of Science and ICT for application of the developed methodologies, and the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy Grant DE-FG02-01ER15228 (to P.P.). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Samsung Science and Technology FoundationSSTF-BA1701-12
National Research Foundation of Korea2019H1D3A2A02102948
National Research Foundation of Korea2020R1A2C2008246
National Research Foundation of Korea2020R1A5A1019141
Department of Energy (DOE)DE-FG02-01ER15228
Subject Keywords:Chemical calculations, Mathematical methods, Electron correlation, Excited states, Butadiene
Issue or Number:39
DOI:10.1021/acs.jpclett.1c02707
Record Number:CaltechAUTHORS:20211008-224623371
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20211008-224623371
Official Citation:Internal Conversion between Bright (11Bu+) and Dark (21Ag–) States in s-trans-Butadiene and s-trans-Hexatriene Woojin Park, Jun Shen, Seunghoon Lee, Piotr Piecuch, Michael Filatov, and Cheol Ho Choi The Journal of Physical Chemistry Letters 2021 12 (39), 9720-9729 DOI: 10.1021/acs.jpclett.1c02707
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:111324
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Oct 2021 14:29
Last Modified:18 Oct 2021 22:30

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