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A comparative ab initio study of the geometry and force field of thionformic acid with formic and thiolformic acids

1981; Elsevier BV; Volume: 76; Issue: 4 Linguagem: Inglês

10.1016/0166-1280(81)85090-7

1872-7999

Philip George, Charles W. Bock, Ann Schmiedekamp,

Spectroscopy and Quantum Chemical Studies

The energy and force field for the planar cis and trans conformers of thionformic acid have been calculated using the 4–31 G basis set, augmented by a complete set of d-functions on the sulfur atom, with full geometry optimization. Extensive comparisons are made between the changes in geometry and selected force constants in going from cis- (chain) to the trans- (ring) structures of thionformic, thiolformic and formic acid. These changes are discussed in terms of a hydrogen bonding type of interaction in the OH⋯S, SH⋯O and OH⋯O structural units respectively. Of the thioacid conformers, the trans-thiol is found to be the most stable; the trans-thion and cis-thiol both about 10 kJ mol−1 less stable; and the cis-thion the least stable by about 38 kJ mol−1.