Hartree-Fock Wavefunctions, Potential Curves, and Molecular Properties for OH−(1Σ+) and SH−(1Σ+)

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Abstract
The potential curves for OH−(1σ22σ23σ21π4, X 1Σ+) and SH−(1σ22σ23σ2 1π44σ25σ22π4, X 1Σ+) have been calculated using electronic wavefunctions which are believed to be very near the Hartree‐Fock wavefunctions in accuracy. Using a Dunham analysis for these two potential curves and from internal regularities of percent errors for the ground states of the first‐ and second‐row hydrides, AH, it is predicted that for OH− 19.1≤Be≤19.4 cm−1, 3733≤ωe≤3820 cm−1, and 1.81≤Re≤1.83 bohr and for SH− 9.36≤Be≤9.54 cm−1, 2642≤ωe≤2692 cm−1, and 2.54≤Re≤2.57 bohr. The potential curves of OH− and SH− are thus closely parallel to the potential curves of OH (X 2Πi) and SH (X 2Πi), respectively. Several ways of estimating the electron affinity (E.A.) of OH and SH are presented; the most reliable values are E.A. (OH) = 1.91 eV and E.A. (SH) = 2.25 eV. These calculated results for OH− are in good agreement with recent photodetachment measurements by Branscomb. The electric dipole and quadrupole moments, the electric field gradient at the nuclei, the electronic force acting at the nuclei, and several molecular expectation values are presented as a function of internuclear separation for OH− and SH−. The relationships of these various properties to the analogous properties of the parent neutral systems [OH(X 2Πi) and SH (X 2Πi)] and the isoelectronic systems [HF (X 1Σ+) and HCl (X 1Σ+)] are discussed.

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