title: Water in toluene revisited: vibrational patterns in the stretching region.
abstract: The symmetric (v1) and antisymmetric (v3) stretching bands of water monomers in toluene are revisited using two approaches: (i) calculation of dipole autocorrelation functions (ii) the solvatochromic behaviour of both vibration frequency shifts. The time constants extracted from the autocorrelations account for meaningful differences between the couplings established by the antisymmetric and symmetric vibrations with the solvent. The dipole autocorrelation function for the symmetric stretching band fits well a Lorentzian spectral density and shows a higher contribution to hindered rotation relatively to the one obtained from the antisymmetric stretching. The spectral shifts of stretching frequencies in toluene and in other relevant solvents were interpreted as arising from the electronic and orientational polarisations. Characteristic donor/acceptor interactions also contribute to the red shift and were tested by using empirical solvent basicity scales such as Kamlet-Taft beta and the recently proposed SB. The deviations detected in toluene as regards the continuum dielectric predictions are quantitatively treated and account for the specific interaction between the water and the molecular pi electron system referred to in the literature.
authors.affiliation: Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Lisboa, Portugal.
authors.forename: J A
authors.initials: JA
authors.lastname: Ferreira
authors.forename: L M
authors.initials: LM
authors.lastname: Ilharco
authors.forename: S M
authors.initials: SM
authors.lastname: Costa
mesh_terms: D007700:Kinetics; D012399:Rotation; D012997:Solvents; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013997:Time Factors; D014050:Toluene / Q000737:chemistry*; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D012997:Solvents; D014867:Water; D014050:Toluene