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Issue 19, 2010
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Vibronic coupling in indole: II. Investigation of the 1La1Lb interaction using rotationally resolved electronic spectroscopy

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Abstract

High-resolution electronic spectra of indole (C8H7N) and their detailed analysis are reported. Thirteen low-lying vibronic bands—from the electronic origin transition at 35 231.4 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. The natural lifetimes of the individual vibronic states have also been determined. 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.

Graphical abstract: Vibronic coupling in indole: II. Investigation of the 1La–1Lb interaction using rotationally resolved electronic spectroscopy

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Publication details

The article was received on 26 Jan 2010, accepted on 20 Mar 2010 and first published on 19 Apr 2010


Article type: Paper
DOI: 10.1039/C001778G
Citation: Phys. Chem. Chem. Phys., 2010,12, 4980-4988
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    Vibronic coupling in indole: II. Investigation of the 1La1Lb interaction using rotationally resolved electronic spectroscopy

    J. Küpper, D. W. Pratt, W. Leo Meerts, C. Brand, J. Tatchen and M. Schmitt, Phys. Chem. Chem. Phys., 2010, 12, 4980
    DOI: 10.1039/C001778G

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