title: Overtone spectroscopy of sulfonic acid derivatives.
abstract: Vapor-phase OH-stretching overtone spectra of methanesulfonic acid and trifluoromethanesulfonic acid were recorded in the Deltav(OH) = 4 and 5 regions using cavity ring-down spectroscopy. We compare these spectra to those of sulfuric acid to consider the effect on vibrational overtone spectra of replacing one of the OH groups with a more or less electronegative group. We complement our experimental work with anharmonic oscillator local mode calculations of the OH-stretching frequencies and intensities. The presence of a weak intramolecular interaction between the hydrogen atom of the OH group and the oxygen atom of the adjacent S=O group in methanesulfonic acid lowers its OH-stretching frequency from what would otherwise be predicted based on the electronegativity of the methyl group.
authors.affiliation: Department of Chemistry, University of Otago, Dunedin, New Zealand.
authors.forename: Joseph R
authors.initials: JR
authors.lastname: Lane
authors.forename: Henrik G
authors.initials: HG
authors.lastname: Kjaergaard
authors.forename: Kathryn L
authors.initials: KL
authors.lastname: Plath
authors.forename: Veronica
authors.initials: V
authors.lastname: Vaida