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Ab initio total energy study of brucite, diaspore and hypothetical hydrous wadsleyite

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Abstract

Ab initio total energy calculations based on the local density approximation (LDA) and the generalised gradient approximation (GGA) of density functional theory have been performed for brucite, Mg(OH)2, diaspore, AlOOH and hypothetical hydrous wadsleyite, Mg7Si4O14(OH)2. The use of a general gradient approximation (GGA) is essential to obtain a good agreement (≈ 1%) of the calculated lattice parameters to diffraction data. The calculated fractional coordinates of brucite and diaspore are in good agreement (≈ 1.5%) with experimental data. The angle of the non-linear hydrogen bond in diaspore is reproduced well, and the calculated Raman active OH stretching frequency in brucite is in very good agreement with spectroscopic data. There are no significant differences between the calculated fractional coordinates and the second derivative of the energy when GGA is used instead of standard LDA. It is concluded that the description of the static and the dynamic behavior of the OH groups in these hydroxides is very good. It is therefore inferred that the parameter free model is predictive and it has been used to evaluate a hypothetical structure of hydrous wadsleyite. The model reproduces the unusual Si-O bond length of 1.7 Å, observed in β-Mg2SiO4. It predicts an O-H distance of 0.97 Å, which is significantly shorter than the distance obtained from earlier model calculations.

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Authors and Affiliations

  1. Mineralogisch-Petrographisches Institut der Christian-Albrechts Universität, Olshausenstr. 40, D-24098, Kiel, Germany

    B. Winkler

  2. Molecular Simulations Ltd., 240/250 The Quorum, Barnwell Road, CB5 8RE, Cambridge, UK

    V. Milman

  3. Laboratoire Leon Brillouin, CEN Saclay, F-91191, Gif-sur-Yvette, France

    B. Hennion

  4. Cavendish Laboratory, University of Cambridge, Madingley Road, CB3 0HE, Cambridge, UK

    M. C. Payne & M. -H. Lee

  5. Royal Institution, Albemarle Street, London, UK

    J. S. Lin

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  1. B. Winkler
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  2. V. Milman
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  3. B. Hennion
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  4. M. C. Payne
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  5. M. -H. Lee
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  6. J. S. Lin
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Winkler, B., Milman, V., Hennion, B. et al. Ab initio total energy study of brucite, diaspore and hypothetical hydrous wadsleyite. Phys Chem Minerals 22, 461–467 (1995). https://doi.org/10.1007/BF00200324

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  • DOI: https://doi.org/10.1007/BF00200324

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