Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning

Abstract

A covalent chemical bond carries the connotation of overlap of atomic orbitals between bonded atoms, leading to a buildup of the electron density in the internuclear region. Stabilization of the valence 5f orbitals as the actinide series is crossed leads, in compounds of the minor actinides americium and curium, to their becoming approximately degenerate with the highest occupied ligand levels and hence to the unusual situation in which the resultant valence molecular orbitals have significant contributions from both actinide and the ligand yet in which there is little atomic orbital overlap. In such cases, the traditional quantum-chemical tools for assessing the covalency, e.g., population analysis and spin densities, predict significant metal-ligand covalency, although whether this orbital mixing is really covalency in the generally accepted chemical view is an interesting question. This review discusses our recent analyses of the bonding in AnCp3 and AnCp4 (An = Th-Cm; Cp = η(5)-C5H5) using both the traditional tools and also topological analysis of the electron density via the quantum theory of atoms-in-molecules. I will show that the two approaches yield rather different conclusions and suggest that care must be taken when using quantum chemistry to assess metal-ligand covalency in this part of the periodic table. The implications of this work for minor actinide partitioning from nuclear wastes are discussed; minor actinide extractant ligands based on nitrogen donors have received much attention in recent years, as have comparisons of the extent of covalency in actinide-nitrogen bonding with that in analogous lanthanide systems via quantum-chemical studies employing the traditional tools for assessing the covalency.