Hemi bonds and noncovalent interactions in the cational systems (XH2P: SHY)+

Quantum chemistry ab initio MP2 and CCSD calculations were performed to investigate the P center dot center dot center dot S hemi bonds and noncovalent interactions in the radical cational systems (H3P:SH2)(+), (FH2P:SH2)(+) and (H3P:SHF)(+). The hydride dimer (H3P:SH2)(+) has a P center dot center dot center dot S hemi bonding structure and a H-bonding structure, (FH2P:SH2)(+) has two hemi bonding structures and a proton-transferred H-bonding structure, (H3P:SHF)(+) has two hemi bonding structures and three noncovalent structures. It is remarkable that these hemi bonds also have characters of pnicogen and chalcogen bonds. The binding energy, stability and bonding nature of the hemi bonds were presented. (C) 2016 Elsevier B.V. All rights reserved.