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Disordering of MgAl2O4 spinel from first principles

Published online by Cambridge University Press:  05 July 2018

M. C. Warren ,
M. T. Dove  and
S. A. T. Redfern
M. C. Warren*
Affiliation:
Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge, CB2 3EQ, UK
M. T. Dove
Affiliation:
Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge, CB2 3EQ, UK
S. A. T. Redfern
Affiliation:
Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge, CB2 3EQ, UK
*
*E-mail: [email protected]
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Abstract

At high temperature, MgAl2O4 spinel is stabilized by disorder of Mg and Al between octahedral and tetrahedral sites. This behaviour has been measured up to 1700 K in recent neutron experiments, but the extrapolation of subsequently fitted thermodynamic models is not reliable. First principles simulation of the electronic structure of such minerals can in principle accurately predict disorder, but would require unfeasibly large computing resources. We have instead parameterized on-site and short-ranged cluster potentials using a small number of electronic structure simulations at zero temperature. These potentials were then used in large-scale statistical simulations at finite temperatures to predict disordering thermodynamics beyond the range of experimental measurements. Within the temperature range of the experiment, good agreement is obtained for the degree of order. The entropy and free energy are calculated and compared to those from macroscopic models.

Keywords

disorderspinelneutron experimentelectronic structure calculationMonte Carlo
Type
Research Article
Information
Mineralogical Magazine , Volume 64 , Issue 2 , April 2000 , pp. 311 - 317
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2000

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References

Clarke, L.J., Stich, I. and Payne, M.C. (1992) Large-scale ab initio total energy calculations on parallel computers. Comp. Phys. Comms., 72, 14–28.CrossRefGoogle Scholar
Dove, M.T. (1997) Theory of displacive phase transitions in minerals. Amer. Mineral., 82, 213–44.CrossRefGoogle Scholar
Dove, M.T., Thayaparam, S., Heine, V. and Hammonds, K.D. (1996) The phenomenon of low Al-Si ordering temperatures in aluminosilicate framework structures. Amer. Mineral., 81, 349–62.CrossRefGoogle Scholar
Myers, E.R., Heine, V. and Dove, M.T. (1998) Thermodynamics of Al/Al avoidance in the ordering of Al/Si tetrahedral framework structures. Phys. Chem. Min., 25, 457–64.CrossRefGoogle Scholar
O’Neill, H. and Navrotsky, A. (1983) Simple spinels: crystallographic parameters, cation radii, lattice energies, and cation distribution. Amer. Mineral., 68, 181–94.Google Scholar
Payne, M.C., Teter, M.P., Allan, D.C., Arias, T.A. and Joannopoulos, J.D. (1992) Iterative minimisation techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients. Rev. Mod. Phys., 64, 1045–97.CrossRefGoogle Scholar
Redfern, S.A.T., Harrison, R.J., O’Neill, H.St.C. and Wood, D.R.R. (1999) Thermodynamics and kinetics of cation ordering in MgAl2O4 spinel up to 1600° from in situ neutron diffraction. Amer. Mineral., 84, 299–310.CrossRefGoogle Scholar
Thayaparam, S., Heine, V., Dove, M.T. and Hammonds, K.D. (1996) A computational study of Al/Si ordering in cordierite. Phys. Chem. Min., 23, 127–39.CrossRefGoogle Scholar
Warren, M.C., Redfern, S.A.T. and Dove, M.T. (2000) Ab initio simulations of cation ordering in oxides: application to spinel. J. Phys.: Cond. Mat., 12, L43–L48.Google Scholar
Wood, B.J., Kirkpatrick, R.J. and Montez, B. (1986) Order-disorder phenomena in MgAl2O4 spinel. Amer. Mineral., 71, 999–1006.Google Scholar
Yeomans, J.M. (1992) Statistical Mechanics of Phase Transitions. Oxford University Press, New York.Google Scholar