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Molecular dynamics simulations of pressure and temperature effects on MgSiO3 and Mg2SiO4 melts and glasses

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Abstract

Ab-initio interionic potentials for Mg2+, Si4+, and O2− have been used in molecular dynamics (MD) simulations to investigate diffusivity changes, pressure-induced structural transitions, and temperature effects on polymerization in MgSiO3 and Mg2SiO4 melts and glasses. The potential gives reasonable agreement with the 0.1 MPa radial distribution function of MgSiO3 glass. Maxima in the diffusion coefficients of Si4+ and O2− occur as pressure is increased on the MgSiO3 melt. The controlling structural mechanism for this behavior is the Q1 species of SiO4 tetrahedra. Mg2+ diffusion coefficients decrease monotonically with pressure in both melt compositions. Increasing Mg2+ coordination number and population of 3- and 4-membered SiO4 rings with pressure combine to hinder translation of the Mg2+ ions. The dominant changes in structure with pressure are a decrease in the intertetrahedral (Si-O--Si) angle up to approximately 4 g/cm3 and coordination changes of the ions above this density. Temperature effects on viscosity in these simulated melts are indirectly studied by analyzing polymerization changes with temperature. Polymerization and coordination numbers increase with decreasing temperature and a small quench rate effect is observed. Fair agreement is found between the MD simulations and experimental equation of state for Mg2SiO4, but the equation of state predictions for MgSiO3 melts are much less accurate. The zero pressure volume, V 0, is significantly higher and K 0 is lower in the simulations than empirical values. The inadequacies reflect error in using the ionic approximation for polymerized systems and a need to collect more data for a variety of molecular configurations in the development of ab-initio potentials.

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Authors and Affiliations

  1. Geophysical Laboratory, Carnegie Institution of Washington, 20015, Washington, DC, USA

    J. D. Kubicki

  2. Department of Geology and Geophysics, Yale University, 06511, New Haven, CT, USA

    A. C. Lasaga

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  1. J. D. Kubicki
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  2. A. C. Lasaga
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Kubicki, J.D., Lasaga, A.C. Molecular dynamics simulations of pressure and temperature effects on MgSiO3 and Mg2SiO4 melts and glasses. Phys Chem Minerals 17, 661–673 (1991). https://doi.org/10.1007/BF00202236

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  • DOI: https://doi.org/10.1007/BF00202236

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