title: High-resolution ultraviolet spectroscopy of p-fluorostyrene-water: evidence for a sigma-type hydrogen-bonded dimer.
abstract: Ab initio calculations predict four stable conformational structures of the singly hydrated cluster of p-fluorostyrene: two out of plane with pi- and two in plane with sigma-type intermolecular hydrogen bonding between p-fluorostyrene and water. We employed mass-selective resonance-enhanced two-photon ionization high-resolution (70-MHz FWHM laser bandwidth) spectroscopy to partially resolve the rotational structure of the 0(0) (0) origin band of the S(1) <--S(0) electronic transition. A computer-aided fit based on genetic algorithms was used to analyze the experimental high-resolution spectrum and to determine the observed conformational structure. The good agreement between the experimental and the simulated spectra of the 0(0) (0) band and the assignment of the other prominent bands as inter- and intramolecular vibrational progressions clearly demonstrates that the anti in-plane conformer is the most abundant one in the molecular beam. The existence of the sigma-type hydrogen bond between p-fluorostyrene and water manifests that the electron attracting effect of fluorine dominates over the releasing mesomeric effect of the vinyl group and thus a pi-type hydrogen bonding with the aromatic ring is not favored in this case.
authors.affiliation: Physikalische und Theoretische Chemie, Technische Universität München, Garching, Germany.
authors.forename: S
authors.initials: S
authors.lastname: Chervenkov
authors.forename: P Q
authors.initials: PQ
authors.lastname: Wang
authors.forename: J E
authors.initials: JE
authors.lastname: Braun
authors.forename: S
authors.initials: S
authors.lastname: Georgiev
authors.forename: H J
authors.initials: HJ
authors.lastname: Neusser
authors.forename: Chayan K
authors.initials: CK
authors.lastname: Nandi
authors.forename: Tapas
authors.initials: T
authors.lastname: Chakraborty