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Electronic Spectra and Reversible Photoisomerization of Protonated Naphthalenes in Solid Neon

Garkusha, Iryna and Nagy, Adam and Fulara, Jan and Rode, Michal F. and Sobolewski, Andrzej L. and Maier, John P.. (2013) Electronic Spectra and Reversible Photoisomerization of Protonated Naphthalenes in Solid Neon. The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, and general theory, Vol. 117, H. 2. pp. 351-360.

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Official URL: http://edoc.unibas.ch/dok/A6194506

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Abstract

Alpha- and beta-protonated naphthalenes (α- and β-HN+) were investigated by electronic absorption and fluorescence spectroscopies in 6 K neon matrixes using a mass-selected C10H9+ ion beam. The absorption spectra reveal S1/S2 ← S0 transitions with onsets at 502.1 and 396.1 nm for α-HN+, and 534.5 and 322.3 nm in the case of β-HN+. Wavelength-dispersed fluorescence was detected for α-HN+, starting at 504.4 nm. Light-induced α-HN+ → β-HN+ isomerization was observed upon S2 ← S0 excitation of α-HN+, whereas β-HN+ relaxed back into the more stable alpha form either upon excitation to S1 or via thermal population of the ground state vibrational levels near the top of the energy barrier between the two isomers. The intramolecular proton transfer leading to the α-HN+ ↔ β-HN+ photoisomerization is fully reversible. The observations are explained with the support of theoretical calculations on the ground- and excited states of the isomers, vertical excitation and adiabatic energies, minimum-energy pathways along the relevant reaction coordinates, and conical intersections between the electronic states.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Maier)
UniBasel Contributors:Maier, John Paul and Roth, Iryna and Fulara, Jan and Nagy, Adam
Item Type:Article, refereed
Article Subtype:Research Article
Bibsysno:Link to catalogue
Publisher:American Chemical Society
ISSN:1089-5639
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:06 Dec 2013 09:35
Deposited On:06 Dec 2013 09:35

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