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Monte Carlo and Molecular Dynamics Simulation of Uranyl Adsorption on Montmorillonite Clay

Published online by Cambridge University Press:  01 January 2024

Omar F. Zaidan ,
Jeffery A. Greathouse  and
Roberto T. Pabalan
Omar F. Zaidan
Affiliation:
Department of Chemistry, St. Lawrence University, Canton, NY 13617, USA
Jeffery A. Greathouse*
Affiliation:
Department of Chemistry, St. Lawrence University, Canton, NY 13617, USA
Roberto T. Pabalan
Affiliation:
Center for Nuclear Waste Regulatory Analyses, Southwest Research Institute, 6220 Culebra Road, San Antonio, TX 78238, USA
*
*E-mail address of corresponding author: [email protected]
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Abstract

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We performed Monte Carlo and molecular dynamics simulations to investigate the interlayer structure of a uranyl-substituted smectite clay. Our clay model is a dioctahedral montmorillonite with negative charge sites in the octahedral sheet only. We simulated a wide range of interlayer water content (0 mg H2O/g clay — 260 mg H2O/g clay), but we were particularly interested in the two-layer hydrate that has been the focus of recent X-ray absorption experiments. Our simulation results for the two-layer hydrate of uranyl-montmorillonite yield a water content of 160 mg H2O/g clay and a layer spacing of 14.66 Å. Except at extremely low water content, uranyl cations are oriented nearly parallel to the surface normal in an outer-sphere complex. The first coordination shell consists of five water molecules with an average U-O distance of 2.45 Å, in good agreement with experimental data. At low water content, the cations can assume a perpendicular orientation to include surface oxygen atoms in the first coordination shell. Our molecular dynamics results show that UO2(H2O)52+ complexes translate within the clay pore through a jump diffusion process, and that first-shell water molecules are exchangeable and interchangeable.

Keywords

Computer SimulationMolecular DynamicsMonte CarloMontmorilloniteUranyl
Type
Research Article
Information
Clays and Clay Minerals , Volume 51 , Issue 4 , August 2003 , pp. 372 - 381
Copyright
Copyright © 2003, The Clay Minerals Society

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