Covalency in AnCl3(An = Th-No)

Abstract

The geometric and electronic structures of AnCl3are studied computationally using scalar relativistic, hybrid density functional theory (PBE0). The An-Cl bond lengths generally decrease across the 5f series, although there is a slight lengthening from Fm-Cl to No-Cl as the metal ions display increasing M(ii) character. Covalency in the An-Cl bond is studied using a wide range of metrics drawn from the Natural Bond Orbital, Natural Resonance Theory and Quantum Theory of Atoms-in-Molecules (QTAIM) methods, including bond order, orbital composition, orbital overlap and electron density topology data. Most metrics agree that the later An-Cl bonds are less ionic than might be anticipated on the basis of trends in the first half of the series, due to energy degeneracy-driven covalency in the β spin manifold; for example, the An-Cl QTAIM delocalisation index (bond order) for MdCl3(0.88) is almost exactly the same as for NpCl3(0.89). By contrast, the ratio of the kinetic to potential energy densities at the An-Cl bond critical points indicates that ionicity increases across the series, suggesting that the delocalisation index measures both orbital overlap and energy degeneracy-based covalency, while the bond critical point metric gauges only the former. Recalculation of all the data using the generalised gradient approximation PBE functional finds larger energy degeneracy-driven covalency in the later actinides than using hybrid DFT. Hence, we find that conclusions concerning the covalency of the An-Cl bond are dependent not only on the metric used to evaluate it, but also on the underlying electronic structure method.