Resonance Raman and density functional study of the A-band absorption of C5H5[WC≡CPh]O2

Abstract

Resonance Raman spectra including absolute Raman cross-section measurements and density functional theory (DFT) calculations were performed to study the A-band absorption of C 5H 5[WCCPh]O 2. The three most intense Franck-Condon active modes, the nominal W=O stretch, C=C stretch and CC stretch, show noticeable intensity in their overtones as well as their combination bands with each other. This is consistent with the changes in the HOMO-LUMO electron densities obtained from the DFT calculations. This suggests that the excited-state experiences significant structural changes simultaneously in the W=O, C=C and CC groups and the charge transfer is delocalized in the electronic transition. © 2001 Elsevier Science B.V.