%0 Journal Article
%A Pinacho, Pablo
%A Perez Cuadrado, Cristobal
%A Stahn, Marcel
%A Saragi, Rizalina T.
%A Hansen, Andreas
%A Grimme, Stefan
%A Lesarri, Alberto
%A Schnell, Melanie
%T Hydrogen Bond Interaction Networks in the Mixed Pentamers of Hydrogen Sulfide and Water
%J Journal of the American Chemical Society
%V 147
%N 22
%@ 0002-7863
%C Washington, DC
%I ACS Publications
%M PUBDB-2025-04980
%P 18576 - 18582
%D 2025
%X The observation of gas-phase water clusters has been instrumental in understanding water aggregation and cooperativity, paving the way for solvation models in the bulk. However, the characterization of hydrogen sulfide self-aggregation is still largely unexplored. Here, we investigate two mixed pentamers of hydrogen sulfide and water to examine the influence of the weaker, dispersion-based and less directional interactions caused by hydrogen sulfide. Unprecedented structural resolution was obtained by combination of jet-cooled broadband rotational spectroscopy and quantum-chemical calculations. Specifically, we compare the 4:1 and 1:4 hydrogen sulfide - water pentamers, offering comparison with the prototype homoclusters. Important structural differences are revealed in the hydrogen sulfide clusters, which reorganize to compensate for the weaker sulfur-centered hydrogen bonds. The noncovalent interactions in the pentamers were rationalized using density functional theory and reduced electronic density calculations. Moreover, a comprehensive many-body decomposition energy analysis revealed significant variations in molecule two- and three-body contributions to the total interaction energy based on the relative proportions of H<sub>2</sub>O and H<sub>2</sub>S. These findings offer new insights into the distinct cooperative forces in water and hydrogen sulfide clusters. The results will improve our understanding and modeling of sulfur-centered hydrogen bonds, which may be useful across various research fields, including protein folding, molecular aggregation, materials science, and computational benchmarking.
%F PUB:(DE-HGF)16
%9 Journal Article
%R 10.1021/jacs.4c18276
%U https://bib-pubdb1.desy.de/record/641249