چکیده
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This work presents an ab initio study on
chalcogen–hydride interactions in several binary com-
plexes of chalcogen-containing molecules with HXeH. The
geometries, H–Xe stretching frequencies and interaction
energies of XCYHXeH binary complexes are investi-
gated at MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ
levels of theory, where X = O, S, Se, Te and Y = S, Se,
Te. For each XCYHXeH complex, a chalcogen–hydride
bond is formed between the negatively charged hydrogen
atom of the HXeH molecule and the most positive elec-
trostatic potential region (r-hole) on the surface of the
interacting atom Y. Upon complex formation, a notable
blue shift is found for the H–Xe stretch vibration. This
result reveals that there is a stronger H
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(XeH)
?
ion-pair
character in XCYHXeH complexes than in free HXeH
molecule. In order to shed light on the origin of the
chalcogen–hydride interactions, molecular electrostatic
potential, quantum theory of atoms in molecules and
interaction energy decomposition analyses are performed.
Cooperative effects between a conventional chalcogen
bond and the chalcogen–hydride interaction in
OCYOCYHXeH complexes are also investigated.
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