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Description of Sudden Polarization in the Excited Electronic States with an Ensemble Density Functional Theory Method

Filatov, Michael and Lee, Seunghoon and Choi, Cheol Ho (2021) Description of Sudden Polarization in the Excited Electronic States with an Ensemble Density Functional Theory Method. Journal of Chemical Theory and Computation, 17 (8). pp. 5123-5139. ISSN 1549-9618. doi:10.1021/acs.jctc.1c00479.

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Sudden polarization (SP) is one of the manifestations of electron transfer in the electronically excited states of molecules. Proposed initially to explain the unusual reactivity of photoexcited olefins, SP often occurs in the excited states of molecules possessing strongly correlated diradical ground state. Theoretical description of SP involves mixing between the singly excited and the doubly excited zwitterionic states, which makes it inaccessible with the use of the popular linear-response time-dependent density functional theory methods. In this work, an extended variant of the state-interaction state-averaged spin-restricted ensemble-referenced Kohn–Sham (SI-SA-REKS, or SSR) method is applied to study SP in a number of organic diradical systems. To this end, the analytical derivative formalism is derived and implemented for the SSR(3,2) method (see the main text for explanation of the acronym), which enables the automatic geometry optimization and obtains the relaxed density matrices as well as the electron binding energies and respective Dyson’s orbitals. Application of the new method to SP in the lowest singlet excited state of ethylene agrees with the results obtained previously with the use of multireference methods of wavefunction theory. A number of interesting manifestations of SP are observed, such as the charge transfer in photoexcited tetramethyleneethene (TME) diradical mediated by the vibrational motion and conductivity switching in the excited state of a donor–acceptor dyad placed in an external electric field.

Item Type:Article
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URLURL TypeDescription
Filatov, Michael0000-0002-1541-739X
Lee, Seunghoon0000-0003-3665-587X
Choi, Cheol Ho0000-0002-8757-1396
Additional Information:© 2021 The Authors. Published by American Chemical Society. ACS AuthorChoice - Attribution-NonCommercial-NoDerivs 2.0 Generic (CC BY-NC-ND 2.0) Received: May 14, 2021. M.F. was supported by the National Research Foundation of Korea (NRF) Grant 2019H1D3A2A02102948. C.H.C. was supported by the Samsung Science and Technology Foundations Grant SSTF-BA1701-12 and the NRF Grants 2020R1A2C2008246 and 2020R1A5A1019141. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Research Foundation of Korea2019H1D3A2A02102948
Samsung Science and Technology FoundationSSTF-BA1701-12
National Research Foundation of Korea2020R1A2C2008246
National Research Foundation of Korea2020R1A5A1019141
Subject Keywords:Hydrocarbons, Electrical energy, Mathematical methods, Excited states, Molecules
Issue or Number:8
Record Number:CaltechAUTHORS:20210730-180911511
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Official Citation:Description of Sudden Polarization in the Excited Electronic States with an Ensemble Density Functional Theory Method. Michael Filatov, Seunghoon Lee, and Cheol Ho Choi. Journal of Chemical Theory and Computation 2021 17 (8), 5123-5139; DOI: 10.1021/acs.jctc.1c00479
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110104
Deposited By: Tony Diaz
Deposited On:02 Aug 2021 17:00
Last Modified:16 Aug 2021 17:21

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