Nodeless Valence (Pseudo)spinors

Atomic calculations using small-core relativistic effective core potentials (RECPs) explicitly treating outer core electrons are used to define two-component nodeless valence spinors (NVSs) and nodeless valence pseudospinors (NVPSs). Errors attributable to nonlocal electron repulsion interactions that arise from large-core RECPs are shown to result from the inherent arbitrariness in the choice of match points and number of derivatives that define shape-consistent pseudospinors, as well as the positions of radial nodes that reside in the outer core regions of atoms. Self-consistent field calculations in ωω-coupling for InH and InCl using RECPs derived from NVSs and NVPSs are reported. Increased bond distances relative to those calculated using very-large-core RECPs for In agree with those due to frozen 4d_3/2 and 4d_5/2 spinors and a small-core RECP. Results for AmCl+2 also reveal that the shortening in the bond length is recovered when the very-large-core RECP is derived using nodeless valence (pseudo)spinors.