Threshold Collision-Induced Dissociation of Hydrogen-Bonded Dimers of Carboxylic Acids

Abstract

Energy-resolved competitive collision-induced dissociation is used to investigate the proton-bound heterodimer anions of a series of carboxylic acids (formic, acetic, and benzoic acid) and nitrous acid with their conjugate bases. The dissociation reactions of the complexes [CH₃COO·H·OOCH]^–, [CH₃COO·H·ONO]^–, [HCOO·H· ONO]^–, [C₆H₅COO·H·OOCH]^–, and [C₆H₅COO·H·ONO]^– are investigated using a guided ion beam tandem mass spectrometer. Cross sections of the two dissociation channels are measured as a function of the collision energy between the complex ions and xenon target gas. Apparent relative gas-phase acidities are found by modeling the cross sections near the dissociation thresholds using statistical rate theory. Internal inconsistencies are found in the resulting relative acidities. These deviations apparently result from the formation of higher-energy conformers of the acids within the complex ions induced by double hydrogen bonding, which impedes the kinetics of dissociation to ground-state product acid conformations.