Probing Elusive Cations: Infrared Spectroscopy of Protonated Acetic Acid

Protonated carboxylic acids, (RCOOH)­H⁺, are the initial intermediates in acid-catalyzed (Fischer) esterification reactions. However, the identity of the isomeric form has been debated. Surprisingly, no optical spectra have been reported for any isomer of the protonated carboxylic acid monomer, despite it being a fundamental organic cation. Here, we address these issues by using a new approach to prepare cold He-tagged cations of protonated acetic acid (AA), which entails electron ionization of helium nanodroplets containing metastable dimers of AA. The protonated species is subsequently probed using infrared photodissociation spectroscopy, and following a comparison with calculations, we identify the two isomers whose roles in Fischer esterification are debated. These are the carbonyl-protonated E,Z isomer and the metastable hydroxyl-protonated isomer. Our technique provides a novel approach that can be applied to other elusive ionic species.