United-Atom Approximation Applied to Argonlike Molecules. I. Hydrogen Sulfide

Abstract

The united‐atom approximation was applied to H₂S and also to the systems HS^— and S^——. The wavefunction obtained for H₂S was used to calculate the molar diamagnetic susceptibility and the coherent x‐ray scattering factor for the gaseous form of the molecule. Values are also reported for the ``breathing'' force constant for H<sub>2</sub>S and for the theoretical bond length for both H<sub>2</sub>S and HS<sup>—</sup>. Within the present approximation a calculation was made of the bond energy for H<sub>2</sub>S dissociating into HS and S. The proton affinities for HS<sup>—</sup> and S<sup>——</sup> were also determined. Where possible, a comparison was made with experiment. In general, except for the proton affinities and bond‐energy calculation, the united‐atom model applied to H<sub>2</sub>S was reasonably successful. A comparison was also made between the present radial density and the density of electrons for H<sub>2</sub>S provided by the model of ``floating'' hydrogen densities. This comparison helps to substantiate the claim made earlier, namely, that the model of ``floating'' hydrogen densities will provide a very reasonable radial distribution of electrons within molecules of the form XH_n.