Infrared action spectroscopy of the deprotonated formic acid trimer, trapped in helium nanodroplets

• Published in: Physical chemistry chemical physics : PCCP 2023-04, Vol.25 (15), p.197-1916
• Main Authors: Taccone, Martín I, Thomas, Daniel A, Ober, Katja, Gewinner, Sandy, Schöllkopf, Wieland, Meijer, Gerard, von Helden, Gert
• Format: Article
• Language: English
• Subjects: Acids; Carboxylic acids; Dimers; Electronic structure; Formic acid; Functional groups; Helium; Hydrogen bonding; Infrared spectroscopy; Line spectra; Planar structures; Protons; Spectra; Spectrum analysis; Trimers
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp05409d

Hydrogen bonding interactions are essential in the structural stabilization and physicochemical properties of complex molecular systems, and carboxylic acid functional groups are common participants in these motifs. Consequently, the neutral formic acid (FA) dimer has been extensively investigated in the past, as it represents a useful model system to investigate proton donor-acceptor interactions. The analogous deprotonated dimers, in which two carboxylate groups are bound by a single proton, have also served as informative model systems. In these complexes, the position of the shared proton is mainly determined by the proton affinity of the carboxylate units. However, very little is known about the nature of the hydrogen bonding interactions in systems containing more than two carboxylate units. Here we report a study on the deprotonated (anionic) FA trimer. IR spectra are recorded in the 400-2000 cm −1 spectral range by means of vibrational action spectroscopy of FA trimer ions embedded in helium nanodroplets. Characterization of the gas-phase conformer and assignment of the vibrational features is achieved by comparing the experimental results with electronic structure calculations. To assist in the assignments, the 2 H and 18 O FA trimer anion isotopologues are also measured under the same experimental conditions. Comparison between the experimental and computed spectra, especially the observed shifts in spectral line positions upon isotopic substitution of the exchangeable protons, suggests that the prevalent conformer, under the experimental conditions, exhibits a planar structure that resembles the crystalline structure of formic acid. Hydrogen bonding interactions are essential in the structural stabilization and physicochemical properties of complex molecular systems, and carboxylic acid functional groups are common participants in these motifs.