Calculation of Spinndash;Orbit Coupling Constants and Other Radial Parameters for the Actinide Ions Using Relativistic Wavefunctions

摘要

Relativistic selfhyphen;consistent Diracndash;Slater and Diracndash;Fock wavefunctions have been used to evaluate the spinndash;orbit coupling constant and matrix elements ofrnfor most of the actinide ions and neutral atoms. Empirical corrections for the Diracndash;Slaterzgr;5fconstants based on experimental results are suggested which enable one to predict freehyphen;ion values more accurately. Values ofzgr;5ffrom crystal and solution spectra show reductions from these estimates which are independent of atomic numberZ, but vary roughly according to ionic charge and ligand electronegativity. It is shown thatlang;rminus;3rang;parameters from atomic beam measurements on Sm, Eu, Pu, and Am can be accounted for fairly well with relativistic Diracndash;Slater wavefunctions and intermediate coupling eigenvectors; configuration interaction, core polarization, and other contributions to hyperfine coupling are neglected. Similar calculations with hyperfine coupling constants from crystal EPR spectra are less consistently satisfactory.