Quantum mechanical vs. empirical potential modeling of uranium dioxide (UO2) surfaces: (111), (110), and (100)
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Frances N. Skomurski
,
Rodney C. Ewing
Abstract
To evaluate the stability, potential reactivity, and relaxation mechanisms on different uraninite surfaces, surface energy values were calculated and structural relaxation was determined for the (111), (110), and (100) crystallographic faces of uranium dioxide (UO2) using quantum mechanical (density functional theory) and empirical potential computational methods. Quantum mechanical results are compared with empirical potential results, which use surface slab models with two different geometries, as well as various different empirical force fields. The strengths and weaknesses of the different approaches are evaluated, and surface stabilizing mechanisms such as relaxation, charge redistribution, and electronic stabilization are investigated. Quantum mechanical (q.m.) surface energy results are in agreement with the relative surface energy trends resulting from calculations using three different empirical potential sets for uranium and oxygen (two from Catlow 1977; one from Meis and Gale 1998), and with empirical force-field values published in the literature (Abramowski et al. 1999, 2001). The (111) surface consistently has the lowest surface energy (0.461 J/m2 from q.m. calculations) and the smallest amount of surface relaxation, followed by the (110) surface (0.846 J/m2; q.m.), and the (100) surface (1.194 J/m2; q.m.) (quantum mechanical surface energy values in parentheses are for surface slabs with a thickness of four UO2 units). Differences exist, however, in the absolute values of surface energies calculated as a function of potential set used. Quantum mechanical values are consistently lower than values calculated using empirical potential methods. A fourth potential set is presented that is derived from fitting electrostatic and short-range repulsive parameters to experimental bulk properties and surface energies and relaxations from quantum mechanical calculations.
© 2015 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- Presidential Address to the Mineralogical Society of America, Salt Lake City, October 18, 2005: Mineral surfaces and the prebiotic selection and organization of biomolecules
- A rare garnet-tourmaline-sillimanite-biotite-ilmenite-quartz assemblage from the granulite-facies region of south-central Massachusetts
- Effects of natural radiation damage on back-scattered electron images of single crystals of minerals
- Thermal diffusivity of olivine-group minerals at high temperature
- Quantum mechanical vs. empirical potential modeling of uranium dioxide (UO2) surfaces: (111), (110), and (100)
- AXANES study of Cu speciation in high-temperature brines using synthetic fluid inclusions
- A new approach to determine and quantify structural units in silicate glasses using micro-reflectance Fourier-Transform infrared spectroscopy
- Titanium incorporation and VITi3+ -IVTi4+ charge transfer in synthetic diopside
- Hugoniot and impact-induced phase transition of magnesite
- Finite element modeling of elastic volume changes in fluid inclusions: Comparison with experiment
- Thermodynamics of mixing in pyrope-grossular, Mg3Al2Si3O12-Ca3Al2Si3O12, solid solution from lattice dynamics calculations and Monte Carlo simulations
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- New insight into crystal chemistry of topaz: A multi-methodological study
- Tetrahedrally coordinated boron in tourmalines from the liddicoatite-elbaite series from Madagascar: Structure, chemistry, and infrared spectroscopic studies
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- New experimental data on biotite + magnetite + sanidine saturated phonolitic melts and application to the estimation of magmatic water fugacity
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- Depolymerization effect of water in aluminosilicate glasses: Direct evidence from 1H-27Al heteronuclear correlation NMR
- Hydroxylellestadite from Cioclovina Cave (Romania): Microanalytical, structural, and vibrational spectroscopy data
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