Visible photodissociation spectra of the 1- and 2-methylnaphthalene cations: laser spectroscopy and theoretical simulations.

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 D-2 <- D-0 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.