Abstract
The electronic structure of isothiocyanic acid, HNCS, was determined by an ab initio LCAO‐MO‐SCF calculation. Isocyanic acid, HNCO, was also calculated and the two molecules are compared. The basis set consisted of uncontracted, atom‐optimized Gaussian functions, with nine s plus five p exponents to describe the sulfur and five s plus two p apiece for the carbon, nitrogen, and oxygen. The hydrogen was represented by three s‐type functions. An additional calculation of HNCS was carried out by adding a d set to the description of the sulfur. The molecular orbitals of HNCS are analyzed using simple perturbation theory applied to the localized valence‐bond functions and the SCF orbitals are displayed using planar electron‐density plots. The electronic structure of HNCS is compared with that of HNCO and it is concluded that (1) the π system in HNCS involves a nitrogen lone pair stabilized by a higher‐lying C–S π bond while the π system of HNCO consists of a C–O π bond stabilized by the higher‐energy nitrogen lone pair and (2) the d orbitals of sulfur are accepting density in a σ rather than a π fashion.
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