RELATIVISTIC SELF-CONSISTENT-FIELD CALCULATIONS OF SPIN ORBIT SPLITTINGS IN DIATOMIC HYDRIDES

Spin-orbit splittings in a few diatomic hydrides are calculated as the differences between total energies of two Ω states of 2Π by the relativistic self-consistent-field method using Slater type functions as basis functions. The dependence of the spin-orbit splittings on the size and quality of basis sets is investigated and an optimal strategy for the selection of the basis set in the all-electron relativistic self-consistent-field calculation is suggested-Dipole moments are also calculated for the hydrides and the effects of the relativity and the spin-orbit coupling on dipole moments are discussed. The variation of the spin-orbit splittings with internuclear distances is investigated for the OH molecule. The present method is capable of yielding proper basis set limits and the calculations with a basis set of moderate size yield qualitatively good results although the Breit interaction term is omitted. The effects of the Breit term on the spin-orbit splittings are estimated to be considerably less than those of two-electron spin-orbit interaction terms. © 1990 American Institute of Physics.