Valence activity of SO-coupled atomic core shells in solid compounds of heavy elements.

A close inspection 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 [ThO] and a series of [UO] 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-[UO], with medium short U-O distances and high 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 findings open up new possibilities for electronic material applications.