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Modulation of the L-a/L-b Mixing in an Indole Derivative: A Position Dependent Study Using 4-, 5-, and 6-Fluoroindole

Autor(en)
Josefin Wilke, Martin Wilke, Christian Brand, J. Dominik Spiegel, Christel M. Marian, Michael Schmitt
Abstrakt

The lowest two electronically excited singlet states of indole and its derivatives are labeled as L-a or L-b, based on the orientation of the transition dipole moment (TDM) and the magnitude of the permanent electric dipole moment. Rotationally resolved electronic Stark spectroscopy in combination with high level ab initio calculations offers the possibility to determine these characteristics and thus the electronic nature of the excited states. In the present contribution this approach was pursued for the systems 4- and 6-fluoroindole and the results compared to the previously investigated system 5-fluoroindole. Changing the position of the fluorine atom from 5 to 4 or 6 is accompanied by an increasing amount of L-a character in the S-1 state. This dramatically influences the orientation of the TDM and erases its ability to be a reasonable identifier of the nature of the excited states for both molecules. However, for 4-fluoroindole, where the influence of the La is weak, the nature of the S1 state can still be assigned to be mainly L-b based on the excited state dipole moment. For 6-fluoroindole, this is not the case anymore, and the L-a/L-b nomenclature completely breaks down due to heavily mixed excited states.

Organisation(en)
Quantenoptik, Quantennanophysik und Quanteninformation
Externe Organisation(en)
Heinrich-Heine-Universität Düsseldorf
Journal
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Band
121
Seiten
1597-1606
Anzahl der Seiten
10
ISSN
1089-5639
DOI
https://doi.org/10.1021/acs.jpca.6b12605
Publikationsdatum
03-2017
Peer-reviewed
Ja
ÖFOS 2012
103025 Quantenmechanik, 104017 Physikalische Chemie
Schlagwörter
ASJC Scopus Sachgebiete
Physical and Theoretical Chemistry
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/a6b31a75-6324-4e24-9a0b-ffd39312d34d