Origins of the odd optical observables in plutonium and americium tungstates

摘要

A series of trivalent f-block tungstates, MW _(2) O _(7) (OH)(H _(2) O) (M = La, Ce, Pr, Nd, and Pu) and AmWO _(4) (OH), have been prepared in crystalline form using hydrothermal methods. Both structure types take the form of 3D networks where MW _(2) O _(7) (OH)(H _(2) O) is assembled from infinite chains of distorted tungstate octahedra linked by isolated MO _(8) bicapped trigonal prisms; whereas AmWO _(4) (OH) is constructed from edge-sharing AmO _(8) square antiprisms connected by distorted tungstate trigonal bipyramids. PuW _(2) O _(7) (OH)(H _(2) O) 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 CeW _(2) O _(7) (OH)(H _(2) O), but not for AmWO _(4) (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 PuW _(2) O _(7) (OH)(H _(2) O) and AmWO _(4) (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.