A MEAN-FIELD SPIN-ORBIT METHOD APPLICABLE TO CORRELATED WAVE-FUNCTIONS

Starting from the full microscopic Breit-Pauli or no-pair spin-orbit H amiltonians, we have devised an effective one-electron spin-orbit Hami ltonian in a well defined series of approximations by averaging the tw o-electron contributions to the spin-orbit matrix element over the val ence shell. In addition the two-electron integrals were restricted to comprise only one-centre terms. The validity of these approximations h as been tested on several palladium containing compounds. Excellent ag reement of the matrix elements of the mean-field operator with corresp onding full results is observed; deviations amount to a few cm(-1) in absolute value or at most 0.2% on a relative scale. The newly defined mean-field operator can thus safely be employed to evaluate spin-orbit effects in transition metal containing compounds.