Mixed H2S and H2O Clusters─New Insights into Dispersion-Dominated Hydrogen Bonding

J Phys Chem A. 2024 Nov 7;128(44):9627-9633. doi: 10.1021/acs.jpca.4c05510. Epub 2024 Oct 24.

Abstract

Here, we report the results of an IR spectroscopy study on heteroclusters of H2S and H2O and several of their isotopomers using mass-selective IR spectroscopy in superfluid helium nanodroplets in the range of 2560-2800 cm-1. Based on DFT calculations on the B3LYP-D3/6-311++G(d,p) level of theory, we were able to assign the experimentally observed O-D stretching bands to heterodimer and heterotrimer clusters. Since no bands of the S-H-bound conformer HSH···OH2 could be observed, we were able to determine the O-H-bound conformer HOH···SH2 to be the global minimum structure. A trapping of the local minima in helium nanodroplets was not observed. This is in line with the weaker hydrogen bond expected for H2S complexes. In these clusters, the interaction energy is expected to be more dominated by dispersion and less dictated by highly directional electrostatic forces.