Norm-conserving 5f-in-core Pseudopotentials and Gaussian Basis Sets Optimized for Tri- and Tetra-Valent Actinides (An = Pa-Lr)

Abstract

Relativistic pseudopotentials and basis sets are the workhorse for modeling heavy elements of lanthanides and actinides. The norm-conserving Goedecker, Teter, and Hutter (GTH) pseudopotential is advantageous for modeling lanthanides and actinides compounds and condensed systems because of its transferability and accuracy. In this work, we develop a set of well-benchmarked GTH-type 5f-in-core pseudopotentials with scalar-relativistic effects, together with associated Gaussian basis sets for the most commonly encountered trivalent and tetravalent actinides (An(III), An(IV); An = Pa-Lr). The 5f-in-core GTH pseudopotentials are constructed by placing 5f-subconfiguration 5fn open shells of An(III) and 5fn-1 of An(IV) (n = 2-14) into the atomic core in the core-valence separation. The different performances of 5f-in-core GTH pseudopotentials for trivalent and tetravalent actinides are further analyzed from the chemical bonding features of actinides. The formalism of 5f-in-core GTH pseudopotentials circumvent the computational difficulty arising from 5fx open valence shell. The optimized 5f-in-core GTH PPs and Gaussian basis sets can be used to accelerate the costly first-principles modeling of structure-complicated actinide compounds and condensed-phase actinide systems.