title: Determination of the geometry change of the phenol dimer upon electronic excitation.
abstract: 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 fi ve 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 pipi* 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.
authors.affiliation: Heinrich-Heine-Universität, Institut für Physikalische Chemie I, 40225 Düsseldorf, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Brause
authors.forename: Monika
authors.initials: M
authors.lastname: Santa
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
authors.forename: Karl
authors.initials: K
authors.lastname: Kleinermanns