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The Intermolecular SH⋅⋅⋅Y (Y=S,O) Hydrogen Bond in the H 2 S Dimer and the H 2 S–MeOH Complex
Author(s) -
Bhattacherjee Aditi,
Matsuda Yoshiyuki,
Fujii Asuka,
Wategaonkar Sanjay
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201201012
Subject(s) - dimer , hydrogen bond , chemistry , water dimer , crystallography , intermolecular force , acceptor , infrared spectroscopy , spectroscopy , photochemistry , molecule , physics , condensed matter physics , organic chemistry , quantum mechanics
Abstract The nature of the SH⋅⋅⋅S hydrogen‐bonding interaction in the H 2 S dimer and its structure has been the focus of several theoretical studies. This is partly due to its structural similarity and close relationship with the well‐studied water dimer and partly because it represents the simplest prototypical example of hydrogen bonding involving a sulfur atom. Although there is some IR data on the H 2 S dimer and higher homomers from cold matrix experiments, there are no IR spectroscopic reports on SH⋅⋅⋅S hydrogen bonding in the gas phase to‐date. We present experimental evidence using VUV ionization‐detected IR‐predissociation spectroscopy (VUV‐ID‐IRPDS) for this weak hydrogen‐bonding interaction in the H 2 S dimer. The proton‐donating SH bond is found to be red‐shifted by 31 cm −1 . We were also able to observe and assign the symmetric ( ν 1 ) stretch of the acceptor and an unresolved feature owing to the free SH of the donor and the antisymmetric ( ν 3 ) SH stretch of the acceptor. In addition we show that the heteromolecular H 2 S–MeOH complex, for which both SH⋅⋅⋅O and OH⋅⋅⋅S interactions are possible, is S‐H⋅⋅⋅O bound.