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"Ultrafast proton transfer of 1-hydroxy-2-acetonaphthone: Reaction path from resonance Raman and transient absorption studies" S. Lochbrunner, A. Szeghalmi, K. Stock, and M. SchmittJ. Chem. Phys. 122, 244315 (2005) Abstract: The intramolecular degrees of freedom contributing to the ultrafast excited state intramolecu-lar proton transfer of 1-hydroxy-2-acetonaphthone are determined. Thereto resonance Raman studies are combined with transient absorption measurements with 30 fs time resolution. En-hanced Raman intensity is found in coordinates that are dominantly associated with deforma-tions and bond length changes in the naphthalene chromophore. This indicates that the primary changes after the optical excitation are a geometric relaxation of the chromophore. A ringing of the molecule after the ultrafast proton transfer is observed by the transient absorption measurements. It reveals the nuclear coordinates contributing to the reaction path beyond the Franck-Condon region. There, planar H-chelate ring deformations changing the donor acceptor distance are found to dominate. The difference in the observed vibrational signatures indicates a significant turn in the reaction path. BMO authors (in alphabetic order): Stefan Lochbrunner |