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          Institute: MPI für biophysikalische Chemie     Collection: Spektroskopie und photochemische Kinetik (Prof. Jürgen Troe)     Display Documents



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ID: 17069.0, MPI für biophysikalische Chemie / Spektroskopie und photochemische Kinetik (Prof. Jürgen Troe)
Fluorescence excitation spectrum, lifetimes and photoisomerization of jet-cooled conformers of 1,1 '- bi(benzocyclobutylidene)
Authors:Ernst, D.; Rupp, L.; Frank, R.; Kuehnle, W.; Lemmen, P.; Lenoir, D.; Schroeder, J.; Grimm, C.; Steinel, T.
Language:English
Date of Publication (YYYY-MM-DD):2002
Title of Journal:Zeitschrift für Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics
Volume:216
Start Page:555
End Page:574
Review Status:Peer-review
Audience:Not Specified
Abstract / Description:First measurements of fluorescence excitation spectra of the recently synthesized rigid stilbene analogue 1,1'- bi(benzocyclobutylidene) in a supersonic jet expansion show that, in contrast to the parent compound, both the trans- and the cis-conformer fluoresce under these conditions. The excitation energy dependence of fluorescence lifetimes indicates the onset of an efficient non-radiative decay channel above energy thresholds of 1340 cm(-1) and 990 cm(-1) for the trans- and cis-form, respectively, which is assigned to photoisomerization in the singlet state. From an RRKM analysis of the microcanonical rate coefficients an estimate of the high pressure limit of the thermal photoisomerization rate coefficient is obtained and compared with photoisomerization rate coefficients measured in low viscosity solution and in thermal vapor. There are strong indications that for this compound there are no dynamic or static solvent induced effects that lead to an anomalous acceleration of the reaction in solution.
Comment of the Author/Creator:Date: 2002
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für biophysikalische Chemie/Abt. Jürgen Troe / 010
External Affiliations:Univ Gottingen, Inst Phys Chem, Tammannstr 6, D-37077; Gottingen, Germany; Univ Gottingen, Inst Phys Chem, D-37077 Gottingen, Germany; GSF, Forschungszentrum Neuherberg, Inst Okol Chem, D-85758 Oberschleissheim, Germany; Tech Univ Munich, Inst Organ Chem & Biochem, D-85747 Garching, Germany
Identifiers:ISI:000175425000001 [ID No:1]
ISSN:0942-9352 [ID No:2]
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