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On the Additivity of Molecular Fragment Dipole Moments of 5-Substituted Indole Derivatives

Autor(en)
Josefin Wilke, Martin Wilke, Christian Brand, W. Leo Meerts, Michael Schmitt
Abstrakt

The estimate of the magnitude and the orientation of molecular electric dipole moments from the vector sum of bond or fragment dipole moments is a widely used approach in chemistry. However, the limitations of this intuitive model have rarely been tested experimentally, particularly for electronically excited states. Herein, we find rules for a number of indole derivatives by using rotationally resolved electronic Stark spectroscopy and ab initio calculations. Based on a natural-bond-orbital analysis, we discuss whether the vector additivity rule can be applied in a given electronic state. From a comparison of the experimental data with ab initio calculations, we deduced that the additivity model does not apply when the flow of electron density from the substituent is opposed to that inside the chromophore.

Organisation(en)
Quantenoptik, Quantennanophysik und Quanteninformation
Externe Organisation(en)
Heinrich-Heine-Universität Düsseldorf, Radboud University
Journal
ChemPhysChem: a European journal of chemical physics and physical chemistry
Band
17
Seiten
2736-2743
Anzahl der Seiten
8
ISSN
1439-4235
DOI
https://doi.org/10.1002/cphc.201600420
Publikationsdatum
09-2016
Peer-reviewed
Ja
ÖFOS 2012
104017 Physikalische Chemie
Schlagwörter
ASJC Scopus Sachgebiete
Atomic and Molecular Physics, and Optics, Physical and Theoretical Chemistry
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/e70d38b6-5360-4168-b824-2cd89c98fde3