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

ABSTRACT: 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 [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 O _h 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 split

SUBMITTER: Wei SR 

PROVIDER: S-EPMC11934502 | biostudies-literature | 2025 Apr

REPOSITORIES: biostudies-literature