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Determination of the Geometry Change of the Phenol Dimer upon Electronic Excitation
Ist Teil von
Chemphyschem, 2007-06, Vol.8 (9), p.1394-1401
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2007
Link zum Volltext
Quelle
Wiley Online Library Journals Frontfile Complete
Beschreibungen/Notizen
The change of the phenol dimer (PH2) structure upon electronic excitation is determined by a Franck–Condon analysis of the intensities in the fluorescence emission spectra obtained via excitation of seven different vibronic bands. A total of 547 emission band intensities are fitted, together with the changes of rotational constants upon electronic excitation of five isotopomers. These rotational constants are taken from previously published [Schmitt et al. ChemPhysChem 2006, 7, 1241–1249] high‐resolution LIF measurements. The geometry change upon electronic excitation of the ππ* state of the donor moiety can be described by a strong shortening of the hydrogen bond, a shortening of the CO bond in the donor moiety, an overall symmetric expansion of the donor phenol ring, and a nearly unchanged acceptor moiety. The resulting geometry changes are interpreted on the basis of ab initio calculations.
Analysing phenol: The structural changes of phenol upon electronic excitation are quantified experimentally and theoretically. A Franck–Condon analysis of the fluorescence emission spectra confirms the local nature of the excitation.