Laser spectroscopic investigation of salicylic acids hydrogen bonded with water in supersonic jets: Microsolvation effects for excited state proton dislocation.

Geometric structures and excited-state proton dislocation of size-selected salicylic acid clusters (salicylic acid and 5-methoxysalicylic acid) with water were studied by using laser spectroscopic techniques. Fluorescence excitation, dispersed fluorescence, and infrared (IR) spectra of those clusters in supersonic jets were examined for both the electronic ground (S0) and first excited (S1) states. The geometric structures of the clusters were determined on the basis of the IR spectra of the OH stretch region with the help of quantum chemical calculations. The hydroxyl group of the water moiety in the clusters forms a ring involving the carboxylic group of the salicylic acid moiety. The IR spectra in S0 show that the intramolecular hydrogen bond in the salicylic acid moiety is still held upon cluster formation, but the phenolic OH stretch band intensity is remarkably weaken in the clusters. The IR spectra in the S1 state and dispersed fluorescence spectra indicated that the intramolecular excited state proton dislocation is hardly affected by the microsolvation with water, in contrast with the strong suppression of the dislocation in the self-solvation.