Origins of the odd optical observables in plutonium and americium tungstates

Abstract

A series of trivalent f-block tungstates, MW₂O₇(OH)(H₂O) (M = La, Ce, Pr, Nd, and Pu) and AmWO₄(OH), have been prepared in crystalline form using hydrothermal methods. Both structure types take the form of 3D networks where MW₂O₇(OH)(H₂O) is assembled from infinite chains of distorted tungstate octahedra linked by isolated MO₈ bicapped trigonal prisms; whereas AmWO₄(OH) is constructed from edge-sharing AmO₈ square antiprisms connected by distorted tungstate trigonal bipyramids. PuW₂O₇(OH)(H₂O) crystallizes as red plates; an atypical color for a Pu(III) compound. Optical absorption spectra acquired from single crystals show strong, broadband absorption in the visible region. A similar feature is observed for CeW₂O₇(OH)(H₂O), but not for AmWO₄(OH). Here we demonstrate that these significantly different optical properties do not stem directly from the 5f electrons, as in both systems the valence band has mostly O-2p character and the conduction band has mostly W-5d character. Furthermore, the quasi-particle gap is essentially unaffected by the 5f degrees of freedom. Despite this, our analysis demonstrates that the f-electron covalency effects are quite important and substantially different energetically in PuW₂O₇(OH)(H₂O) and AmWO₄(OH), indicating that the optical gap alone cannot be used to infer conclusions concerning the f electron contribution to the chemical bond in these systems.