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Ab Initio study of the electrostatic multipole nature of torsional potentials in CH 3 SSCH 3 , CH 3 SSH, and HOOH
Author(s) -
Sokalski W. A.,
Lai J.,
Luo N.,
Sun S.,
Shibata M.,
Ornstein R.,
Rein R.
Publication year - 1991
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560400711
Subject(s) - multipole expansion , ab initio , ab initio quantum chemistry methods , atomic physics , computational chemistry , electrostatics , physics , chemistry , molecular physics , quantum mechanics , molecule
The origin of torsional potentials in H 3 CSSCH 3 , H 3 CSSH, and HOOH and the anisotropy of the local charge distribution has been analyzed in terms of atomic multipoles calculated from the ab initio LCAO – MO – SCF wave function in the 6–31G* basis set. The results indicate that for longer SS‐bonds the major contribution to these torsional barriers are electrostatic interactions of the atomic multipoles located on two atoms forming the rotated bond. This finding demonstrates the important role of electrostatic 1–2 interatomic interactions, usually neglected in conformational studies. It also opens the possibility to derive directly from accurate ab initio wave functions a simple nonempirical torsional potential involving atomic multipoles of two bonded atoms defining the torsional angle. For shorter OO bonds, use of more precise models and inclusion of 1–3 interactions seems to be necessary.