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

ID: 472535.1, Fritz-Haber-Institut / Molecular Physics
Vibronic coupling in indole:
I. Theoretical description of the ¹La-¹Lb interaction and the
electronic spectrum
Authors:Brand, Christian; Küpper, Jochen; Pratt, David. W.; Meerts, W. Leo; Krügler, Daniel; 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:4968
End Page:4979
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:The properties of the three lowest singlet electronic states (ground, ¹Lb, and ¹La state) of indole (C₈H₇N) have been calculated with second-order approximate coupled-cluster theory (CC2) within
the resolution-of-the-identity approximation. Refined electronic energies at the CC2 optimized structures and transition dipole moments were calculated using a density-functional theory multireference configuration-interaction (DFT/MRCI) approach. Structures, energies, and dipole moments are reported for all three states and compared to experimental values. From the optimized structures and calculated transition dipole moments, we predict that pure ¹Lb bands will have positive signs for both the axis reorientation angle θT and the angle θ of the transition dipole moment with respect to the inertial a axis. For ¹La bands the signs of both angles will be reversed. Vibronically coupled bands can exhibit opposite signs for θ and θT. The absorption and emission spectra of indole are calculated based on the Franck-Condon Herzberg-Teller approximation using numerical transition dipole moment derivatives at the DFT/MRCI level of theory. Implications for the experimentally observed vibronic spectra are discussed. Predictions are made for rotationally resolved spectra of various rovibronic bands. A conical intersection, connecting the ¹Lb and ¹La states, which can be accessed to varying extents via different Herzberg-Teller active modes is found approximately 2000cm-1 above the ¹Lb minimum.

External Publication Status:published
Document Type:Article
Communicated by:Gerard Meijer
Affiliations:Fritz-Haber-Institut/Molecular Physics
External Affiliations:Heinrich-Heine-Universität, Institut für Physikalische Chemie I, 40225 Düsseldorf, Germany;
University of Pittsburgh, Department of Chemistry, Pittsburgh, PA 15260, USA;
Radboud University Nijmegen, Institute for Molecules and Materials, Heyendaalseweg 135, NL-6525 AJ Nijmegen, The Netherlands;
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