TY  - JOUR
AU  - Pinacho, Pablo
AU  - Perez Cuadrado, Cristobal
AU  - Stahn, Marcel
AU  - Saragi, Rizalina T.
AU  - Hansen, Andreas
AU  - Grimme, Stefan
AU  - Lesarri, Alberto
AU  - Schnell, Melanie
TI  - Hydrogen Bond Interaction Networks in the Mixed Pentamers of Hydrogen Sulfide and Water
JO  - Journal of the American Chemical Society
VL  - 147
IS  - 22
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2025-04980
SP  - 18576 - 18582
PY  - 2025
AB  - 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.
LB  - PUB:(DE-HGF)16
DO  - DOI:10.1021/jacs.4c18276
UR  - https://bib-pubdb1.desy.de/record/641249
ER  -