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Diffusion of aluminium in MgO from first principles

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Abstract

We have calculated the diffusivity of aluminium in periclase, MgO, under pressures relevant to deep planetary interiors from first principles. We reconcile differences between experimental migration enthalpies and those obtained with previous theoretical studies by finding a lower energy saddle point for the aluminium atom migration. Previous studies did not recognise a bifurcation at the saddle point. We also explain differences between experimental and theoretical binding enthalpies of an aluminium with a magnesium vacancy. We find that binding enthalpies continuously increase with decreasing aluminium concentrations, such that the difference between experimental and theoretical binding energies can be attributed to differing concentrations. We also find that binding energies increase with pressure as the permittivity decreases. Aluminium therefore not only causes extrinsic vacancy formation but also binds some of them, effectively removing them for magnesium diffusion. We discuss the implications for how other 3+ ions affect diffusion in oxides and silicates.

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Acknowledgments

The authors acknowledge the use of UCL Research Computing facilities of Legion and of HECToR, the UK’s national high-performance computing service, which is provided by UoE HPCx Ltd at the University of Edinburgh, Cray Inc and NAG Ltd., and funded by the Office of Science and Technology through EPSRC’s High End Computing Programme.

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  1. Department of Earth Sciences, University College London, Gower Street, London, WC1E 6BT, UK

    M. W. Ammann, J. P. Brodholt & D. P. Dobson

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  1. M. W. Ammann
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  2. J. P. Brodholt
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  3. D. P. Dobson
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Correspondence to M. W. Ammann.

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Ammann, M.W., Brodholt, J.P. & Dobson, D.P. Diffusion of aluminium in MgO from first principles. Phys Chem Minerals 39, 503–514 (2012). https://doi.org/10.1007/s00269-012-0506-z

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  • DOI: https://doi.org/10.1007/s00269-012-0506-z

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