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Exciplex Stabilization in Asymmetric Acene Dimers

Krueger, Rachel A. and Blanquart, Guillaume (2019) Exciplex Stabilization in Asymmetric Acene Dimers. Journal of Physical Chemistry A, 123 (9). pp. 1796-1806. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20190211-080713669

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Abstract

Excimers play an important role in photochemical processes ranging from singlet fission to DNA damage, and the characteristic red-shift in fluorescence spectra associated with excimer formation can provide information about aggregate formation and the orientation of chromophores. When a mixture of chromophores is present, exciplex formation may lead to spectral characteristics distinct from those of either monomer or the corresponding excimers. To predict the effects of aggregation in a system containing a mixture of small acenes, binding energies and minimum-energy geometries have been calculated for three mixed S_1 exciplexes. Benchmark CASSCF/NEVPT2 multireference binding energies of 18.2, 27.7, and 49.3 kJ/mol are reported for the benzene-naphthalene, benzene-anthracene, and naphthalene-anthracene exciplexes, respectively. TDDFT calculations have been performed using a range of exchange-correlation functionals, showing that many functionals perform inconsistently, and the error in binding energy often depends on the character of the monomer excitation from which the exciplex state is derived. Moderate exciplex stabilization observed for the benzene-naphthalene and naphthalene-anthracene exciplexes results from a mixture of charge transfer and exciton delocalization.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpca.8b11461DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.8b11461PublisherSupporting Information
ORCID:
AuthorORCID
Krueger, Rachel A.0000-0002-5457-2931
Blanquart, Guillaume0000-0002-5074-9728
Additional Information:© 2019 American Chemical Society. Received: November 27, 2018; Revised: February 7, 2019; Published: February 11, 2019. R.A.K. acknowledges funding from the NSF Division of Graduate Education (DGE-1745301). The authors thank Qiming Sun for helpful discussions. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
Record Number:CaltechAUTHORS:20190211-080713669
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190211-080713669
Official Citation:Exciplex Stabilization in Asymmetric Acene Dimers. Rachel A. Krueger and Guillaume Blanquart. The Journal of Physical Chemistry A. 2019 123 (9), 1796-1806 DOI: 10.1021/acs.jpca.8b11461
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92815
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Feb 2019 22:43
Last Modified:11 Mar 2019 21:26

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