Presented as part of a commemorative issue for Wolfgang Kiefer on the occasion of his 65th birthday.
The excited-state geometry of 1-hydroxy-2- acetonaphthone: a resonance Raman and quantum chemical study†
Version of Record online: 12 JAN 2006
Copyright © 2006 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy
Special Issue: Commemorative Issue: for Wolfgang Kiefer on the Occasion of his 65th Birthday
Volume 37, Issue 1-3, pages 148–160, January - March 2006
How to Cite
Szeghalmi, A. V., Engel, V., Zgierski, M. Z., Popp, J. and Schmitt, M. (2006), The excited-state geometry of 1-hydroxy-2- acetonaphthone: a resonance Raman and quantum chemical study. J. Raman Spectrosc., 37: 148–160. doi: 10.1002/jrs.1449
- Issue online: 12 JAN 2006
- Version of Record online: 12 JAN 2006
- Manuscript Accepted: 31 AUG 2005
- Manuscript Received: 19 MAY 2005
- Deutsche Forschungsgemeinschaft DFG. Grant Number: SFB 436.
- resonance Raman spectroscopy;
- quantum chemical calculations;
- proton transfer;
- time-dependent analysis
1-Hydroxy-2-acetonaphthone (HAN), an intramolecular proton transfer system, was investigated in the present study by means of quantum chemical calculations and resonance Raman spectroscopy. To determine the Franck–Condon parameters, a time-dependent approach for the analysis of the resonance Raman spectra was applied. About 18 vibrational modes were found to be involved in the initial dynamics of HAN upon photo excitation. Moreover, the excited-state geometry of HAN was optimized at the CASSCF level of theory and the displacement parameters were determined. A very good agreement between the theoretical and experimentally derived parameters was obtained. The vibrations with the highest displacements correspond to stretching and in-plane deformation modes of the naphthalene ring and the conjugated carbonyl group, while the OH stretching mode exhibits no observable enhancement. Hence, a general molecular rearrangement takes place upon photo excitation, where the intramolecular oxygen–oxygen distance reduces corresponding to a redistribution of the electron density. Copyright © 2006 John Wiley & Sons, Ltd.