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Updated: May 3, 2026

Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry
Published on: March 1, 2020
Identification and characterization of the HCl-DMS gas phase molecular complex via infrared spectroscopy and
Nicolai Bork1, Lin Du, Henrik G Kjaergaard
1Department of Chemistry, University of Copenhagen , Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark.
Abstract:
Models of atmospheric aerosol formation are dependent on accurate Gibbs free binding energies (ΔG°) of gaseous acids and bases, but for most acid–base pairs, only ab initio data are available. We report a combined experimental and theoretical study of the gaseous molecular complex of dimethylsulfide (DMS) and HCl. On the basis of infrared spectroscopy and anharmonic local mode calculations, we determine ΔG(295K)° to be between 6.2 and 11.1 kJ mol(–1). We test the performance of MP2 and five often used DFT functionals with respect to this result. M06-2X performs the best, but also the MP2 prediction is within the experimental range. We find that coupled cluster corrections to the electronic energy improves ΔG° estimates if and only if triple excitations are included. These estimates may be further improved by applying vibrational scaling factors to account for anharmonicity. Hereby, all but the PW91 based predictions are within the experimental range.
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