title: Visible photodissociation spectra of the 1- and 2-methylnaphthalene cations: laser spectroscopy and theoretical simulations.
abstract: The electronic absorption spectra of the two methyl derivatives of the naphthalene cation were measured using an argon tagging technique. In both cases, a band system was observed in the visible range and assigned to the D2 ← D0 electronic transition. The 1-methylnaphthalene(+) absorption bands revealed a red shift of 808 cm(-1), relative to those of the naphthalene cation (14,906 cm(-1)), whereas for 2-methylnaphthalene(+) a blue shift of 226 cm(-1) appeared. A short vibrational progression, similar to the naphthalene cation, was also observed for both isomers and found to involve similar aromatic ring skeleton vibrations. Moreover, insights into the internal rotation motion of the methyl group were inferred, although the spectral resolution was not sufficient to fully resolve the substructure. These measurements were supported by detailed quantum chemical calculations. They allowed exploration of the potential energy curves along this internal coordinate, along with a complete simulation of the harmonic Franck-Condon factors using the cumulant Gaussian fluctuations formalism extended to include the internal rotation.
authors.affiliation: Institut des Sciences Moléculaires d'Orsay, CNRS, Université Paris Sud , 91405 Orsay, France.
authors.forename: Hela
authors.initials: H
authors.lastname: Friha
authors.forename: Géraldine
authors.initials: G
authors.lastname: Féraud
authors.forename: Tyler
authors.initials: T
authors.lastname: Troy
authors.forename: Cyril
authors.initials: C
authors.lastname: Falvo
authors.forename: Pascal
authors.initials: P
authors.lastname: Parneix
authors.forename: Philippe
authors.initials: P
authors.lastname: Bréchignac
authors.forename: Zoubeida
authors.initials: Z
authors.lastname: Dhaouadi
authors.forename: Timothy W
authors.initials: TW
authors.lastname: Schmidt
authors.forename: Thomas
authors.initials: T
authors.lastname: Pino
mesh_terms: D007834:Lasers; D008958:Models, Molecular; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D013057:Spectrum Analysis
chemical_list: D009281:Naphthalenes; C031721:naphthalene