Valence Activity of SO-Coupled Atomic Core Shells in Solid Compounds of Heavy Elements

Abstract

An alert look reveals chemically relevant changes from light to heavy elements of the atomic orbital-energy patterns, relevant for both chemical theory and material applications. We have quantum-chemically investigated the geometric and electronic structures of solid [ThO2] and a series of [UO3] phases at a realistic relativistic level, both with and without spin-orbit (SO) coupling. The observable band gap between the occupied O(2p) bonding valence band and the empty U(5f6d) conduction band is smallest for δ-[UO3], with medium short U-O distances and high Oh symmetry. Both Pauli-repulsion of O(2p) by the strongly SO-split U(6p) core, and additional covalent U(6p)-O(2p) mixing, cause a “pushing up from below” (PFB) and a large SO splitting of the valence band of the light element. PFB has been observed in molecular chemistry, but PFB and PFB-induced SO splitting have so far not been considered in solid-state science. Our finding opens new possibilities for electronic material applications.