Spin-orbit coupling constants from semi-empirical wavefunctions

Abstract
The problem of computing spin-orbit coupling constants from wave-functions of a semi-empirical variety are considered specifically for SCF wavefunctions with intermediate neglect of differential overlap. The incorporation of the 1s electrons into a ‘core’ should result in an effective nuclear charge of Z′ = Z - 2·5846 being used in one-electron terms, but for agreement with experiment the results have to be reduced by some 70 per cent. This reduction factor is different for ions. If the multiplicative factor is included good agreement between observed and calculated spin-orbit coupling constants is given.

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