Covalency in actinide(iv) hexachlorides in relation to the chlorine K-edge X-ray absorption structure

Chlorine K-edge X-ray absorption near edge structure (XANES) in actinide(IV) hexachlorides, [AnCl(6)](2-) (An = Th-Pu), is calculated with relativistic multiconfiguration wavefunction theory (WFT). Of particular focus is a 3-peak feature emerging from U toward Pu, and its assignment in terms of donation bonding to the An 5f vs. 6d shells. With or without spin-orbit coupling, the calculated and previously measured XANES spectra are in excellent agreement with respect to relative peak positions, relative peak intensities, and peak assignments. Metal-ligand bonding analyses from WFT and Kohn-Sham theory (KST) predict comparable An 5f and 6d covalency from U to Np and Pu. Although some frontier molecular orbitals in the KST calculations display increasing An 5f-Cl 3p mixing from Th to Pu, because of energetic stabilization of 5f relative to the Cl 3p combinations of the matching symmetry, increasing hybridization is neither seen in the WFT natural orbitals, nor is it reflected in the calculated bond orders. The appearance of the pre-edge peaks from U to Pu and their relative intensities are rationalized simply by the energetic separation of transitions to 6d t(2g)versus transitions to weakly-bonded and strongly stabilized a(2u), t(2u) and t(1u) orbitals with 5f character. The study highlights potential pitfalls when interpreting XANES spectra based on ground state Kohn-Sham molecular orbitals.