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. 2010 May 25;107(21):9519-24.
doi: 10.1073/pnas.0912130107. Epub 2010 May 10.

Quantum Monte Carlo computations of phase stability, equations of state, and elasticity of high-pressure silica

Affiliations

Quantum Monte Carlo computations of phase stability, equations of state, and elasticity of high-pressure silica

K P Driver et al. Proc Natl Acad Sci U S A. .

Abstract

Silica (SiO(2)) is an abundant component of the Earth whose crystalline polymorphs play key roles in its structure and dynamics. First principle density functional theory (DFT) methods have often been used to accurately predict properties of silicates, but fundamental failures occur. Such failures occur even in silica, the simplest silicate, and understanding pure silica is a prerequisite to understanding the rocky part of the Earth. Here, we study silica with quantum Monte Carlo (QMC), which until now was not computationally possible for such complex materials, and find that QMC overcomes the failures of DFT. QMC is a benchmark method that does not rely on density functionals but rather explicitly treats the electrons and their interactions via a stochastic solution of Schrödinger's equation. Using ground-state QMC plus phonons within the quasiharmonic approximation of density functional perturbation theory, we obtain the thermal pressure and equations of state of silica phases up to Earth's core-mantle boundary. Our results provide the best constrained equations of state and phase boundaries available for silica. QMC indicates a transition to the dense alpha-PbO(2) structure above the core-insulating D" layer, but the absence of a seismic signature suggests the transition does not contribute significantly to global seismic discontinuities in the lower mantle. However, the transition could still provide seismic signals from deeply subducted oceanic crust. We also find an accurate shear elastic constant for stishovite and its geophysically important softening with pressure.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Fig. 1.
Fig. 1.
Thermal equations of state of (A) quartz, (B) stishovite and CaCl2, and (C) α-PbO2. The lower sets of curves in each plot are at room temperature and the upper sets are near the melting temperature. Gray shaded curves are QMC results, with the shading indicating one-sigma statistical errors. The dashed lines are DFT results using the WC functional. Symbols represent diamond-anvil-cell measurements (Exp.) (, , , –31).
Fig. 2.
Fig. 2.
Enthalpy difference of the (A) quartz-stishovite, and (B) CaCl2-α-PbO2 transitions. Gray shaded curves are QMC results, with the shading indicating one-sigma statistical errors. The dashed, dot-dashed, and dotted lines are DFT results using the WC, PBE, and LDA functionals, respectively.
Fig. 3.
Fig. 3.
(A) Computed phase boundary of the quartz-stishovite transition. The gray shaded curve is the QMC result, with the shading indicating one-sigma statistical errors. The dashed line is the boundary predicted using WC. The dash-dot and solid lines represent shock (41, 42) analysis, while dotted and dash-dash-dot lines represent thermochemical data (Thermo.) (39, 43). (B) Computed phase boundary of the CaCl2-α-PbO2 transition. Gray shaded curves are QMC results, with the shading indicating one-sigma statistical errors. The dashed, dotted, and dash-dot lines are DFT boundaries using WC, LDA (19), and PBE (19) functionals, respectively. The dark green shaded region and the solid blue line are diamond-anvil-cell measurements (Exp.) (6, 7). The dash-dot-dot line is the boundary inferred from shock data (17). The vertical light blue bar represents pressures in the D” region. Circles drawn on the geotherm (45) indicate a two-sigma statistical error in the QMC boundary.
Fig. 4.
Fig. 4.
Softening of the c11-c12 shear constant for stishovite with pressure. Down triangles and circles are the DMC and VMC results, respectively. Diamonds and up triangles represent DFT results within the WC and LDA (10), respectively. Squares represent radial X-ray diffraction data (11) and stars represent Brillouin scattering data (14). The shear constant in all methods softens rapidly with increasing pressure and becomes unstable near 50 GPa, signaling a transition to the CaCl2 phase.

References

    1. Cohen RE. Bonding and electronic structure of minerals. In: Wright K, Catlow CRA, editors. Microscopic Properties and Processes in Minerals. The Netherlands: Kluwer; 1999. pp. 201–264.
    1. Levien L, Prewitt CT, Weidner DJ. Structure and elastic properties of quartz at pressure. Am Mineral. 1980;65:920–930.
    1. Levien L, Prewitt CT. High-pressure crystal structure and compressibility of coesite. Am Mineral. 1981;66:324–333.
    1. Ross NL, Shu JF, Hazen RM, Gasparik T. High-pressure crystal chemistry of stishovite. Am Mineral. 1990;75:739–747.
    1. Kingma KJ, Cohen RE, Hemley RJ, Mao HK. Transformation of stishovite to a denser phase at lower-mantle pressures. Nature. 1995;374:243–245.

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