HF· · ·H2S Hydrogen-Bonded Clusters as a Model for Probing Subtle Cooperative Effects
- 1State Key Laboratory of Structural Chemistry
- 2Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences
Abstract
Hydrogen-bond (HB) cooperativity is usually analysed for whole networks, and its variation between individual HBs is poorly understood when strong and weak donors coexist. We resolve 126 HBs in 20 neutral cyclic (HF)m(H2S)n clusters (Nmon = m + n = 3–7). The molecular tailoring approach (MTA) at the MP2/aug-ccpVTZ level splits each in-cluster HB energy into an isolated-dimer part and a network-associated (cooperative) part. The mean MTA energies of the F–H· · ·F, F–H· · · S, S–H· · · F and S–H· · · S bonds are 9.03, 8.47, 2.57 and 2.45 kcal mol−1, respectively. The cooperative part averages 2.11 kcal mol−1 per HB and is positive for nearly all HBs. In these structures, it correlates more strongly with HF content than with cluster size and changes little beyond five monomers. The cooperativity gain index, the cooperative part divided by the isolated-dimer energy, identifies fluorine-accepting HBs as the most enhanced, and S–H· · · F bonds stand out among the weakly bound dimers. For HF-donor HBs, the MTA energy correlates strongly with the H· · ·A distance and the electron density at the bond critical point. By the criteria of the quantum theory of atoms in molecules, these HBs are medium-strength interactions with partial covalent character, whereas the H2S-donor HBs are weak closed-shell interactions that local descriptors predict less well. The HB-resolved energies provide reference data for testing interaction models and machine-learning potentials; applying them to atmospheric or astrochemical systems requires further work.
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BibTeX
@misc{patkar2026hydrogenbonded,
title = {{HF· · ·H2S Hydrogen-Bonded Clusters as a Model for Probing Subtle Cooperative Effects}},
author = {Deepak Patkar},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010862/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010862/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - HF· · ·H2S Hydrogen-Bonded Clusters as a Model for Probing Subtle Cooperative Effects
AU - Deepak Patkar
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010862/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010862/v1
AB - Hydrogen-bond (HB) cooperativity is usually analysed for whole networks, and its variation between individual HBs is poorly understood when strong and weak donors coexist. We resolve 126 HBs in 20 neutral cyclic (HF)m(H2S)n clusters (Nmon = m + n = 3–7). The molecular tailoring approach (MTA) at the MP2/aug-ccpVTZ level splits each in-cluster HB energy into an isolated-dimer part and a network-associated (cooperative) part. The mean MTA energies of the F–H· · ·F, F–H· · · S, S–H· · · F and S–H· · · S bonds are 9.03, 8.47, 2.57 and 2.45 kcal mol−1, respectively. The cooperative part averages 2.11 kcal mol−1 per HB and is positive for nearly all HBs. In these structures, it correlates more strongly with HF content than with cluster size and changes little beyond five monomers. The cooperativity gain index, the cooperative part divided by the isolated-dimer energy, identifies fluorine-accepting HBs as the most enhanced, and S–H· · · F bonds stand out among the weakly bound dimers. For HF-donor HBs, the MTA energy correlates strongly with the H· · ·A distance and the electron density at the bond critical point. By the criteria of the quantum theory of atoms in molecules, these HBs are medium-strength interactions with partial covalent character, whereas the H2S-donor HBs are weak closed-shell interactions that local descriptors predict less well. The HB-resolved energies provide reference data for testing interaction models and machine-learning potentials; applying them to atmospheric or astrochemical systems requires further work.
ER -