Covalency in Lanthanides. An X‑ray Absorption Spectroscopy and Density Functional Theory Study of LnCl₆^<i>x</i>– (<i>x</i> = 3, 2)

Abstract

Covalency in Ln–Cl bonds of <i>O</i>_<i>h</i>-LnCl₆^<i>x</i>– (<i>x</i> = 3 for Ln = Ce^III, Nd^III, Sm^III, Eu^III, Gd^III; <i>x</i> = 2 for Ln = Ce^IV) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L_3,2-edge and M_5,4-edge XAS were also used to characterize CeCl₆^<i>x</i>– (<i>x</i> = 2, 3). The M_5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce^III and Ce^IV). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (<i>t</i>_2<i>g</i>* and <i>e</i>_<i>g</i>*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce^III to Ce^IV had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl₆^3– (formally Ln^III), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce^IV 4f-orbital mixing (<i>t</i>_1<i>u</i>* + <i>t</i>_2<i>u</i>*) in CeCl₆^2–. This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl₆^2– (M = Ti, Zr, Hf, U)