Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H2S)n+ clusters in the gas phase

Dandan Wang, Asuka Fujii

Research output: Contribution to journalArticlepeer-review

27 Citations (Scopus)


A two-center three-electron 2c-3e bond (hemi-bond) is a non-classical chemical bond, and its existence has been supposed in radical cation clusters with lone pairs. Though the nature of the hemi-bond and its role in the reactivity of radical cations have attracted great interest, spectroscopic observations of hemi-bonded structures have been very scarce. In the present study, the presence of a stable hemi-bonded core (H2S∴SH2)+ in (H2S)n+ (n = 3-6) in the gas phase is demonstrated by infrared spectroscopy combined with quantum chemical calculations. The spectral features of the free SH stretch of the ion core show that the hemi-bond motif of the ion core is maintained up to the completion of the first H-bonded solvation shell. All of the observed spectra are well reproduced by the minimum energy hemi-bonded isomers, and no sign of the proton-transferred ion core type H3S+-SH, which is estimated to have a much higher energy, is found. Spin density calculations show that the excess charge is almost equally delocalized over the two H2S molecules in the cluster for n = 3 to 6. This also indicates the hemi-bond nature of the (H2S∴SH2)+ ion core and the small impact of the formation of a solvation shell on the ion core.

Original languageEnglish
Pages (from-to)2667-2670
Number of pages4
JournalChemical Science
Issue number4
Publication statusPublished - 2017


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