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Dynamics of benzene excimer formation from the parallel-displaced dimer

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posted on 2019-01-09, 14:49 authored by Thiago M. Cardozo, Andre P. Galliez, Itamar Borges, Felix PlasserFelix Plasser, Adelia J. Aquino, Mario Barbatti, Hans Lischka
Excimers play a key role in a variety of excited-state processes, such as exciton trapping, fluorescence quenching, and singlet-fission. The dynamics of benzene excimer formation in the first 2 ps after S1 excitation from the parallel-displaced geometry of the benzene dimer is reported here. It was simulated via nonadiabatic surface-hopping dynamics using the second-order algebraic diagrammatic construction (ADC(2)). After excitation, the benzene rings take ∼0.5–1.0 ps to approach each other in a parallel-stacked structure of the S1 minimum and stay in the excimer region for ∼0.1–0.4 ps before leaving due to excess vibrational energy. The S1–S2 gap widens considerably while the rings visit the excimer region in the potential energy surface. Our work provides detailed insight into correlations between nuclear and electronic structure in the excimer and shows that decreased ring distance goes along with enhanced charge transfer and that fast exciton transfer happens between the rings, leading to the equal probability of finding the exciton in each ring after around 1.0 ps.

Funding

TMC, IB and HL thank the Brazilian Agency CAPES for support of this work in the framework of the Science without Borders Brazilian Program. MB thanks the support of the Excellence Initiative of Aix-Marseille University (A*MIDEX) and the project Equip@Meso (ANR-10-EQPX-29-01), both funded by the French Government ‘‘Investissements d’Avenir’’ program. MB also acknowledges funding from the WSPLIT project (ANR-17-CE05-0005-01). This work was supported by the Center for Integrated Nanotechnologies (Project No. C2013A0070), an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Los Alamos National Laboratory (Contract DE-AC52-06NA25396) and Sandia National Laboratories (Contract DEAC04-94AL85000).

History

School

  • Science

Department

  • Chemistry

Published in

Physical Chemistry Chemical Physics

Volume

21

Issue

26

Pages

13916-13924

Citation

CARDOZO, T.M. ... et al, 2018. Dynamics of benzene excimer formation from the parallel-displaced dimer. Physical Chemistry Chemical Physics, 21 (26), pp.13916-13924.

Publisher

© Royal Society of Chemistry (RSC)

Version

  • AM (Accepted Manuscript)

Publisher statement

This paper was accepted for publication in the journal Physical Chemistry Chemical Physics and the definitive published version is available at https://doi.org/10.1039/c8cp06354k

Acceptance date

2018-12-13

Publication date

2018-12-13

ISSN

1463-9076

eISSN

1463-9084

Language

  • en

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