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Theoretical Study of Ground- and Excited-State Charge Transfer in Fulvene-Based Donor-Acceptor Systems
Linköping University, Department of Physics, Chemistry and Biology, Bioinformatics. Linköping University, Faculty of Science & Engineering. (Theoretical Chemistry)
Linköping University, Department of Physics, Chemistry and Biology, Bioinformatics. Linköping University, Faculty of Science & Engineering. (Theoretical Chemistry)
2019 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 123, no 31, p. 6660-6673Article in journal (Refereed) Published
Abstract [en]

Donor-acceptor systems based on fulvene as the electron-accepting moiety are typified by exotic, strongly polar electronic structures. In this contribution, ab initio calculations have been performed to explore the ground- and excited-state properties of an archetypal compound of this class, which incorporates the exocyclic carbon atom of fulvene into a tetramethylimidazoline-like five-membered ring. In the electronic ground state, the compound under study has a pronounced zwitterionic character and is best described as consisting of a negatively charged cyclopentadienyl ring linked covalently to a positively charged tetramethylimidazolium ring. Both of these rings can be considered as aromatic. The excess negative charge localized on the cyclopentadienyl ring is highly labile in the photochemical sense: the low-lying valence excited states exhibit varying degrees of reverse charge transfer, whereby electron density is transferred from the cyclopentadienyl ring back onto the tetramethylimidazolium ring. The topographies of the excited-state potential energy surfaces favor rapid and efficient internal conversion at an extended, fulvene-like S1/S0 conical intersection seam. As a consequence, the excited-state lifetime of this compound is predicted to be on the order of 100 fs. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019. Vol. 123, no 31, p. 6660-6673
Keywords [en]
Donor-acceptor systems, Excited states, Aromaticity, Molecular switches, Molecular dynamics
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:liu:diva-159198DOI: 10.1021/acs.jpca.9b02962OAI: oai:DiVA.org:liu-159198DiVA, id: diva2:1340261
Funder
Stiftelsen Olle Engkvist Byggmästare, 184-568Wenner-Gren Foundations, UPD2018-0102Available from: 2019-08-02 Created: 2019-08-02 Last updated: 2019-11-14

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The full text will be freely available from 2020-07-11 08:10
Available from 2020-07-11 08:10

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Publisher's full texthttps://pubs.acs.org/doi/10.1021/acs.jpca.9b02962

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