Transferability of core potentials to f and d states of lanthanide and actinide ions

An analysis is made of the transferability of frozen core potentials of neutral lanthanide and actinide elements to 4f/5f and 5d/6d states of their respective 3+ and 4+ ions. A good description of the orbital spin orbit coupling constants zeta(4f)/zeta(5f) and zeta(5d)/zeta(6d) of the Ln(3+)/ An(4+) ions and of the 4f --> 5d/5f --> 6d transition energies is achieved by using [Kr] / [Xe, 4f] cores. The corresponding relativistic core ab initio model potentials (AIMPs) based on Cowan-Griffin atomic calculations, together with optimized Gaussian valence basis sets, are produced for the lanthanide elements Ce to Lu and for the actinide elements Th to Lr. Results are given for the Ce3+ and Pa4+ free ions and in Ce3+- and Pr3+- doped Cs2NaYCl6 and Pa4+ and U4+- doped Cs2ZrCl6 materials.