Electronic Structure of Diatomic Nickel Sulfide

The nature of the Ni–S bond is investigated due to its role in the absorption of atmospheric Lewis acid gases such as SO₂ and SO₃ onto Ni surfaces. The vibrational frequency and electronic structure of NiS were predicted using CCSD(T), CASSCF, and internally contracted multireference configuration interaction (icMRCI) + Q. 43 density functional theory (DFT) functionals were benchmarked. CASSCF predicted the ground state of NiS to be the ⁵Δ state arising from the 3d⁸(³F)4s² (³F) and 3d⁹(²D)4s (³D) electronic configurations of Ni. When dynamical correlation effects are included at the icMRCI + Q level, the ground state of Ni–S is predicted to be ³Σ^– consistent with the experiment. The vibrational frequency of Ni–S is calculated to be 519.1 cm^–1 at the icMRCI + Q level, in reasonable agreement with the experimental value of 512.68 cm^–1. CCSD(T) predicts the frequency of Ni–S to be 543.2 cm^–1 when extrapolated to the complete basis set (CBS) limit. The Feller–Peterson–Dixon value based on the CCSD(T)/CBS extrapolation for the bond dissociation energy of NiS is 350.6 kJ/mol, within <4 kJ/mol of experiment. Of the 43 DFT functionals, BP86 and O3LYP predicted the vibrational frequency in closest agreement with the experiment. The applicability of DFT to such acid gas systems was further demonstrated by calculating the energy for displacement of NiO by SO to yield NiS and O₂. This displacement energy was calculated to be within experimental error for ∼50% of the DFT functionals, but large differences were also predicted for some functionals.