Vibronic Splitting of the Electronic Origin in Two Conformers of the 3-Tolunitrile Dimer.

Autor: Martini J; Heinrich-Heine-Universität, Institut für Physikalische Chemie I, 40225, Düsseldorf, Germany., Ortlepp J; Heinrich-Heine-Universität, Institut für Physikalische Chemie I, 40225, Düsseldorf, Germany., Henrichs C; Shimadzu Deutschland GmbH, 47269, Duisburg, Germany., Schmitt M; Heinrich-Heine-Universität, Institut für Physikalische Chemie I, 40225, Düsseldorf, Germany.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2024 Nov 18; Vol. 25 (22), pp. e202400509. Date of Electronic Publication: 2024 Sep 30.
DOI: 10.1002/cphc.202400509
Abstrakt: 3-tolunitrile (3-TN) can form three different dimers, which differ in the relative orientation of the methyl groups. We determined the geometry changes of two of these conformers of 3-TN upon electronic excitation via a Franck-Condon fit of the vibronic intensities in the fluorescence emission spectra. Both aromatic rings expand upon electronic excitation, showing a delocalized one-photon excitation of the cluster. The conformer with the smaller center-of-mass distance shows an unusual order of the split components of the electronic origin. We attribute this changed order to the stronger charge transfer contributions to the splitting and a partial breakdown of the point dipole approximation, made in the Frenkel type interaction.
(© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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