Stepwise Solvation of the Intramolecular-Charge-Transfer Molecule p-(Dimethylamino)benzonitrile
Abstract
This paper presents a systematic study of gas-phase p-(N,N-dimethy1amino)benzonitrile (DMABN) both in a supersonic jet expansion and in a thermalized vapor. From the jet studies, the excited- and ground-state vibrational spectra of the isolated molecule are resolved, and the spectroscopy of the stoichiometric complex with water, methanol, ammonia, and acetonitrile in the beam is reported. It is concluded that 1:l complexes are not sufficient for the local perturbation to cause charge separation. At higher temperatures in the jet, we observe emission that we attribute to DMABN self-complexes. Under high pressure and temperature vapor conditions (>30 mTorr, 60 °C), red-shifted fluorescence from DMABN is observed. This is attributed to the charge-transfer state of DMABN in self-complexes.
Additional Information
© 1987 American Chemical Society. Received: May 26, 1987. Publication Date: November 1987. We acknowledge the support of this work from the following granting agencies: National Science Foundation Grant DMR-8521191, Air Force Office of Scientific Research Grant AFOSR-87-0071, and Joint Services Electronics Program 29-85-K-0049. We also thank Professor Rudy Marcus for many informative discussions and Dr. K. Bhattacharya for his assistance.Additional details
- Eprint ID
- 70166
- DOI
- 10.1021/j100308a021
- Resolver ID
- CaltechAUTHORS:20160906-090611348
- NSF
- DMR-8521191
- Air Force Office of Scientific Research (AFOSR)
- 87-0071
- Joint Services Electronics Program
- 29-85-K-0049
- Created
-
2016-09-08Created from EPrint's datestamp field
- Updated
-
2021-11-11Created from EPrint's last_modified field
- Other Numbering System Name
- Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 7562