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Stepwise Solvation of the Intramolecular-Charge-Transfer Molecule p-(Dimethylamino)benzonitrile

Peng, Lawrence W. and Dantus, Marcos and Zewail, Ahmed H. and Kemnitz, Klaus and Hicks, Janice M. and Eisenthal, Kenneth B. (1987) Stepwise Solvation of the Intramolecular-Charge-Transfer Molecule p-(Dimethylamino)benzonitrile. Journal of Physical Chemistry, 91 (24). pp. 6162-6167. ISSN 0022-3654. doi:10.1021/j100308a021.

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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.

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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.
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)87-0071
Joint Services Electronics Program29-85-K-0049
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Arthur Amos Noyes Laboratory of Chemical Physics7562
Issue or Number:24
Record Number:CaltechAUTHORS:20160906-090611348
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Official Citation:Stepwise Solvation of the Intramolecular-Charge-Transfer Molecule p-(Dimethylamino)benzonitrile Lawrence W. Peng, Marcos. Dantus, Ahmed H. Zewail, Klaus. Kemnitz, Janice M. Hicks, and Kenneth B. Eisenthal The Journal of Physical Chemistry 1987 91 (24), 6162-6167 DOI: 10.1021/j100308a021
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70166
Deposited By: Ruth Sustaita
Deposited On:08 Sep 2016 18:35
Last Modified:11 Nov 2021 04:25

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