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Published August 10, 2021 | Published + Supplemental Material
Journal Article Open

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

Abstract

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.

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.

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Published - acs.jctc.1c00479.pdf

Supplemental Material - ct1c00479_si_001.pdf

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Created:
August 20, 2023
Modified:
October 23, 2023