Quasirelativistic energy-consistent 5f-in-core pseudopotentials for pentavalent and hexavalent actinide elements

摘要

Quasirelativistic energy-consistent 5f-in-core pseudopotentials modeling pentavalent (5f n−2 occupation with n = 2–6 for Pa–Am) and hexavalent (5f n−3 occupation with n = 3–6 for U–Am) actinides have been adjusted. Energy-optimized (6s5p4d) and (7s6p5d) valence basis sets contracted to polarized double- to quadruple-zeta quality as well as 2f1g correlation functions have been derived. Corresponding smaller basis sets (4s4p3d) and (5s5p4d) suitable for calculations on actinide(V) and actinide(VI) ions in crystalline solids form subsets of these basis sets designed for calculations on neutral molecules. Calculations using the Hartree–Fock and the coupled-cluster method with single and double excitation operators and a perturbative estimate of triple excitations for actinide pentafluorides show satisfactory agreement with calculations using 5f-in-valence pseudopotentials and experimental data, respectively. However, in the hexavalent case the 5f-in-core approximation seems to reach its limitations except for hexavalent uranium (5f0), where results for both uranium hexafluoride and the uranyl ion deviate only slightly from the 5f-in-valence reference data.