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          Institute: Fritz-Haber-Institut     Collection: Molecular Physics     Display Documents

ID: 472044.1, Fritz-Haber-Institut / Molecular Physics
Vibronic coupling in indole:
II. Experimental investigation of the ¹La-¹Lb interaction
using rotationally resolved electronic spectroscopy
Authors:Küpper, Jochen; Pratt, David. W.; Meerts, W. Leo; Brand, Christian; Tatchen, Jörg; Schmitt, Michael
Date of Publication (YYYY-MM-DD):2010
Title of Journal:Physical Chemistry Chemical Physics
Journal Abbrev.:Phys. Chem. Chem. Phys.
Start Page:4980
End Page:4988
Title of Issue:Molecular Mechanisms of the Photostability of Life
Full name of Issue-Editor(s):Andrzej Sobolewski and Wolfgang Domcke
Copyright:© Royal Society of Chemistry 2010
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:High-resolution electronic spectra of indole (C₈H₇N) and their detailed analysis are reported. Thirteen low-lying vibronic bands – from the electronic origin transition at 35231.4 cm-1 up to 1000 cm-1 above – are recorded with rotational resolution. Besides inertial parameters and inertial defects these spectra yield detailed information, for each individual band, on the transition-dipole-moment orientations in the molecular inertial frame as well as on the reorientation of that inertial frame upon electronic excitation. We also determine the natural lifetimes of the individual vibronic states. Strongly varying orientations of the transition-dipole-moments, unexpected positive inertial defects, and decreasing lifetimes, which are only partly related to increased excitation energy, are observed. These results are clear indications of the interaction of the two lowest electronically excited singlet states (¹Lb and ¹La). Our experimental findings are strongly supported by, and in excellent agreement with, the theoretical description of the interaction of the two electronic states described in the preceding paper. These results provide clear evidence for strong vibronic coupling of the two electronic states ¹Lb and ¹La and for the energetic location of the ¹La-state more than 1000 cm-1 above the ¹Lb vibrationless state.
External Publication Status:published
Document Type:Article
Communicated by:Gerard Meijer
Affiliations:Fritz-Haber-Institut/Molecular Physics
External Affiliations:University of Pittsburgh, Department of Chemistry, Pittsburgh, PA 15260, USA;
Heinrich-Heine-Universität, Institut für Physikalische Chemie I, 40225 Düsseldorf, Germany;
Radboud University Nijmegen, Institute for Molecules and Materials, Heyendaalseweg 135, NL-6525 AJ Nijmegen, The Netherlands;
Chemical Physics Department, Weizmann Institute of Science, 76100 Rehovot, Israel
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