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Ab initio studies of H 2 PXYH molecules (X, Y = O, S)
Author(s) -
Boatz Jerry A.,
Gordon Mark S.
Publication year - 1986
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540070308
Subject(s) - chemistry , intramolecular force , hypervalent molecule , ab initio , lone pair , molecular orbital , crystallography , atomic orbital , molecule , sulfur , computational chemistry , molecular orbital theory , stereochemistry , physics , organic chemistry , reagent , electron , quantum mechanics
Ab initio molecular orbital theory is applied to the study of PO and PS bonding in the hypervalent phosphinic (H 2 POOH), phosphinothioic (H 2 POSH), and phosphinodithioic (H 2 PSSH) acid molecules. Intramolecular proton exchange reactions are followed using the intrinsic reaction coordinate and Self‐Consistent‐Field energy localized orbitals. The PO and PS bonds are characterized via force constants, phosphorus d orbital populations, and localized orbitals and are best described as either normal single bonds or dative bonds augmented by π back donation from the oxygen or sulfur lone pairs. The anions of these acids are also investigated, and they are found to contain only dative bonds to sulfur and oxygen.