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