Die u:cris Detailansicht:
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