title: Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp3 (An = Th-Cm; Cp = η(5)-C5H5).
abstract: The title compounds are studied with scalar relativistic, gradient-corrected (PBE) and hybrid (PBE0) density functional theory. The metal-Cp centroid distances shorten from ThCp(3) to NpCp(3), but lengthen again from PuCp(3) to CmCp(3). Examination of the valence molecular orbital structures reveals that the highest-lying Cp π(2,3)-based orbitals transform as 1e + 2e + 1a(1) + 1a(2). Above these levels come the predominantly metal-based 5f orbitals, which stabilise across the actinide series such that in CmCp(3) the 5f manifold is at more negative energy than the Cp π(2,3)-based levels. Mulliken population analysis shows metal d orbital participation in the e symmetry Cp π(2,3)-based orbitals. Metal 5f character is found in the 1a(1) and 1a(2) levels, and this contribution increases significantly from ThCp(3) to AmCp(3). This is in agreement with the metal spin densities, which are enhanced above their formal value in NpCp(3), PuCp(3) and especially AmCp(3) with both PBE and PBE0. However, atoms-in-molecules analysis of the electron densities indicates that the An-Cp bonding is very ionic, increasingly so as the actinide becomes heavier. It is concluded that the large metal orbital contributions to the Cp π(2,3)-based levels, and enhanced metal spin densities toward the middle of the actinide series arise from a coincidental energy match of metal and ligand orbitals, and do not reflect genuinely increased covalency (in the sense of appreciable overlap between metal and ligand levels and a build up of electron density in the region between the actinide and carbon nuclei).
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London, UK WC1H 0AJ.
authors.forename: Ian
authors.initials: I
authors.lastname: Kirker
authors.forename: Nikolas
authors.initials: N
authors.lastname: Kaltsoyannis