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

Philip George; Charles W. Bock; Ann Schmiedekamp

doi:10.1016/0166-1280(81)85090-7

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

Philip George, Charles W. Bock, Ann Schmiedekamp

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11 Scopus citations

Abstract

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 OH⋯S, SH⋯O and OH⋯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.

Original language	English (US)
Pages (from-to)	363-374
Number of pages	12
Journal	Journal of Molecular Structure: THEOCHEM
Volume	76
Issue number	4
DOIs	https://doi.org/10.1016/0166-1280(81)85090-7
State	Published - Jul 1981

All Science Journal Classification (ASJC) codes

Biochemistry
Condensed Matter Physics
Physical and Theoretical Chemistry

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10.1016/0166-1280(81)85090-7

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

abstract = "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 OH⋯S, SH⋯O and OH⋯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.",

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AU - George, Philip

AU - Bock, Charles W.

AU - Schmiedekamp, Ann

PY - 1981/7

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N2 - 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 OH⋯S, SH⋯O and OH⋯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.

AB - 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 OH⋯S, SH⋯O and OH⋯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.

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

Abstract

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