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Issue 3, 2017
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Structures of protonated hydrogen sulfide clusters, H+(H2S)n, highlighting the nature of sulfur-centered intermolecular interactions

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Abstract

Unique intermolecular structures of protonated hydrogen sulfide clusters, H+(H2S)n, are revealed by infrared spectroscopy and ab initio calculations. The identified intermolecular structures are significantly different from those of the corresponding protonated water clusters, H+(H2O)n, in spite of the common hydrogen bond coordination ability between hydrogen sulfide and water. Protonated hydrogen sulfide clusters have the Eigen type ion core, H3S+, in the size range of n = 3–9. After the first hydrogen bonded shell formation is completed at n = 4, further solvation prefers a new shell bound by the charge–dipole interaction rather than the second hydrogen bonded shell. Thus, closely solvated structures, in which 7 molecules, at maximum, directly interact with the Eigen type ion core, are formed. The beginning of the second hydrogen bonded shell is found at n = 9. Competition among intermolecular interactions in H+(H2S)n is discussed.

Graphical abstract: Structures of protonated hydrogen sulfide clusters, H+(H2S)n, highlighting the nature of sulfur-centered intermolecular interactions

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Article information


Submitted
27 Oct 2016
Accepted
11 Dec 2016
First published
15 Dec 2016

Phys. Chem. Chem. Phys., 2017,19, 2036-2043
Article type
Paper

Structures of protonated hydrogen sulfide clusters, H+(H2S)n, highlighting the nature of sulfur-centered intermolecular interactions

D. Wang and A. Fujii, Phys. Chem. Chem. Phys., 2017, 19, 2036
DOI: 10.1039/C6CP07342E

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