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Issue 26, 2019
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Origins of the odd optical observables in plutonium and americium tungstates

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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.

Graphical abstract: Origins of the odd optical observables in plutonium and americium tungstates

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Publication details

The article was received on 08 Mar 2019, accepted on 17 May 2019 and first published on 21 May 2019


Article type: Edge Article
DOI: 10.1039/C9SC01174A
Chem. Sci., 2019,10, 6508-6518
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Origins of the odd optical observables in plutonium and americium tungstates

    J. N. Cross, T. Lee, C. Kang, Y. Yao, S. K. Cary, J. T. Stritzinger, M. J. Polinski, C. D. McKinley, T. E. Albrecht Schmitt and N. Lanata, Chem. Sci., 2019, 10, 6508
    DOI: 10.1039/C9SC01174A

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