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Structural, mechanical and Raman spectroscopic characterization of the layered uranyl silicate mineral, uranophane-α, by density functional theory methods

Published online by Cambridge University Press:  10 August 2018

Francisco Colmenero Open the ORCID record for Francisco Colmenero [Opens in a new window] ,
Vicente Timón Open the ORCID record for Vicente Timón [Opens in a new window] ,
Laura J. Bonales Open the ORCID record for Laura J. Bonales [Opens in a new window]  and
Joaquín Cobos Open the ORCID record for Joaquín Cobos [Opens in a new window]
Francisco Colmenero*
Affiliation:
Instituto de Estructura de la Materia, CSIC, C/Serrano, 113, 28006 Madrid, Spain
Vicente Timón
Affiliation:
Instituto de Estructura de la Materia, CSIC, C/Serrano, 113, 28006 Madrid, Spain
Laura J. Bonales
Affiliation:
Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, Avda/Complutense, 40, 28040 Madrid, Spain
Joaquín Cobos
Affiliation:
Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas, CIEMAT, Avda/Complutense, 40, 28040 Madrid, Spain
*
*E-mail: francisco.colmenero@iem.cfmac.csic.es
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Abstract

The layered uranyl silicate clay-like mineral, uranophane-α, Ca(UO2)2(SiO3OH)2·5H2O, was studied by first-principles calculations based on the density functional theory method. The structure, observed in nature in a wide variety of compounds having the uranophane sheet anion topology, is confirmed here for the first time by means of rigorous theoretical solid-state calculations. The computed lattice parameters, bond lengths and bond angles were in very good agreement with the experimental ones, and the calculated X-ray powder trace accurately reproduced its experimental counterpart. The mechanical properties of uranophane-α, for which there are no experimental data for terms of comparison, were determined, and the satisfaction of the mechanical stability Born conditions of the structure was demonstrated by calculations of the elasticity tensor. The Raman spectrum was computed by the density functional perturbation theory and compared with the experimental spectrum. The vibrational properties of this mineral were well characterized, showing a good performance in all of the studied spectral range. Theoretical methods allowed assignment of the Raman bands to vibrations localized in different fragments within the crystal unit cell. Finally, the possibility of incorporation of strontium inside the uranophane structure was studied. The computed structure, X-ray powder trace and Raman spectrum of Sr-exchanged uranophane were very close to those of the ordinary Ca-uranophane.

Keywords

spent nuclear fueluranophane-αDFT calculationsuranyl silicate mineralsRaman spectroscopycation exchange

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Type
Article
Information
Clay Minerals , Volume 53 , Issue 3 , September 2018 , pp. 377 - 392
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2018 

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Footnotes

This paper was originally presented during the session OM-05: ‘Computational modeling of clay minerals and related materials' during the International Clay Conference 2017.

Guest Associate Editor: A. Kalinichev

References

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