Exploring single and double proton transfer processes in the gas phase: A high resolution electronic spectroscopy study of 5-fluorosalicylic acid

Abstract

Two species that possess different absorption and emission properties have been observed in the low resolution fluorescence excitation spectrum of 5-fluorosalicylic acid (FSA) in the gas phase. The two species were identified as monomer and dimer species using high resolution techniques. Studies of these spectra in the presence of an applied electric field, together with ab initio quantum chemistry calculations, show that the monomer is a "closed" form of FSA exhibiting an intramolecular C = O⋅⋅⋅H-O-C hydrogen bond in the ground state. Absorption of light at ∼344 nm transforms this species into the tautomeric form C-O-H⋅⋅⋅O = C via a barrierless proton transfer process. The large charge rearrangement that accompanies this process results in a significantly red-shifted emission spectrum. The (FSA)(2) dimer exhibits two intermolecular C=O⋯H-O-C hydrogen bonds but in this case the double proton transfer leads to a conical intersection with the ground state and rapid nonradiative decay. The onset of this process and the time scale on which it occurs are revealed by a homogeneous broadening of the dimer's high resolution spectrum.