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Probing the Thermodynamic Properties of Mantle Rocks in Solid and Liquid States

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The evolutionary path taken by the interior of the Earth is strongly related to the behavior of the rock material from which it is made. Together, these represent the dominant phases of the Earth's mantle, now and in the distant past.

Introduction

These results are then compared to assess the effect of iron composition on the high temperature compression of silicate perovskite. Finally, we assess the plausibility of various competing models to explain the perovskite-rich lower mantle structures.

Methods

Cells were loaded with Ne pressure medium using the GSECARS gas loading system at the Advanced Photon Source (APS) at Argonne National Laboratory ( Rivers et al., 2008 ). The pressure for each spectrum was determined using the Ne pressure medium as a primary pressure marker, Dewaele et al. (2008), along with the offline ruby ​​fluorescence measurements.

Analysis

Peak Fitting

It achieves this by approximately distributing the observed intensities between the diffraction peaks present in each part of the spectrum. This is usually done by assuming a reasonable basic model in terms of unit cell parameters for each spectrum and then locating the diffraction lines that appear to best match the predicted peak positions.

Determining P-T Conditions

In this study, we mainly rely on the diffraction lines of the neon pressure medium to determine the in situ pressures. Through this analysis, we obtain the final determinations of the pressure and its error, calculating the deviatoric stress.

Figure 2.3: Measured spectral temperatures for Fe-bearing sample during laser heating.
Figure 2.3: Measured spectral temperatures for Fe-bearing sample during laser heating.

Extracting Crystal Volumes and Cell Dimensions

We therefore use this model as a prior constraint on the deviatoric stress and refit the set of neon line positions to obtain the best constant for the deviatoric stress fraction for each data set, obtaining values ​​of 0.5% and 0.6% for the Mg end-element and samples, containing Fe, according to the central peaks of the apparent deviatoric stress fraction histograms. By fitting two or three neon lines visible in each spectrum, we obtain unconstrained simultaneous estimates of axial deviatoric stress and neon unit cell size, which are converted to pressure estimates using the neon equation of state from Dewaela et al.

Figure 2.5: The apparent deviatoric stress is plotted against the neon pressure and color coded by temperature, obtained by analyzing the 111, 200, and 220 lines of neon
Figure 2.5: The apparent deviatoric stress is plotted against the neon pressure and color coded by temperature, obtained by analyzing the 111, 200, and 220 lines of neon

Obtaining the Equation of State from P-V-T Measurements

The prior simply expresses the probability distribution for the parameters prior to any particular step of the analysis. This finding is directly reflected in the best-fit estimates for the thermal parameters γ0 and q, which relate to the full scale of thermal expansion and its compression (or volume) dependence.

Table 2.1: Vinet and Mie-Gruneisen-Debye Equation of State Parameters
Table 2.1: Vinet and Mie-Gruneisen-Debye Equation of State Parameters

Discussion

Equation of State Comparison and Uncertainties

First, none of the previous investigations report the full covariance matrix (or equivalent correlation matrix) for their equation of state parameters. In the bottom panel of Figure 2.9, we show the linear evolution of the octahedral tilt angle with compression for the two samples.

Physical Property Profiles

Using these expressions, we determine the isothermal profiles of thermal expansion, bulk modulus and volume for the two perovskite samples. It should be noted that we obtain a significantly different thermal behavior for the Fe-free endmember sample than Fiquet et al. (2000).

Figure 2.8: Comparison of 68% confidence bounds on local properties at core-mantle boundary pressure conditions are shown for Fe-bearing and Fe-free perovskite
Figure 2.8: Comparison of 68% confidence bounds on local properties at core-mantle boundary pressure conditions are shown for Fe-bearing and Fe-free perovskite

Perovskite-Dominated Chemical Piles

In this exercise, use the mixture model described above to calculate the material properties of the mixture at the core-mantle interface. On the left and center of the figure, we show the percent contrast between the mixture model (as a function of composition and temperature) and the main mantle as represented by PREM (Dziewonski and Anderson, 1981). Using a simple linear expansion of the density and the bulk modulus difference at the core-mantle interface, we can obtain rough estimates for the height of the density crossover.

Figure 2.10: Shaded regions show 68% confidence intervals for 300K (light shading) and 3000K (dark shading) isothermal properties of free perovskite in black and 13%  Fe-containing perovskite in red
Figure 2.10: Shaded regions show 68% confidence intervals for 300K (light shading) and 3000K (dark shading) isothermal properties of free perovskite in black and 13% Fe-containing perovskite in red

Conclusion

We can thus assess the relative plausibility of the passive pile and metastable dome explanations by calculating the fraction of the allowed parameter space occupied by material behavior consistent with the two theories—this is simply given by the relative area of ​​the red-shaded region as com. - parried to the white area. This fraction is just below 10%, indicating that while metastable domes may be consistent with our current understanding of the perovskite equation of state, they impose very tight constraints on the temperature-dependent composition of the LLSVP material and are therefore not very likely. Since this intensity weighting map is independent of the collected data, it only needs to be calculated once for each detector configuration.

Introduction

Intro to Bayesian Statistics

As we will show later, the most well-known form of probability uses weighted least squares or. Since the prerequisite for any data analysis problem assumes that we can generate a model for any specific set of model parameters M~, we then use probability distributions for the data points {d} to determine the probability of the data given the model values. We can imagine that we would construct a local first-order Taylor expansion of the physical model in the region of the parameter space that best fits.

Bayesian Analysis of Powder Diffraction Data

Estimating Peak Positions and Uncertainties

We start the fitting process with an initial guess for the peak positions, based on the positions of a few of the most intense and easily identified lines (prior knowledge from previous studies is also useful to obtain a reasonable initial guess). This reflects the fact that the peak width directly controls the relative curvature of the spectrum in the peak region. This well-known result comes from the fact that the expected value of the error-weighted squared residuals is simply equal to one for a normal distribution, h(∆xi/σi)2i = 1.

Figure 3.1: Peak positions for 0% Fe perovskite sample are plotted against pressure in the top panel and against V −1/3 in the bottom panel
Figure 3.1: Peak positions for 0% Fe perovskite sample are plotted against pressure in the top panel and against V −1/3 in the bottom panel

Estimating Unit Cell Parameters and Accounting for Misidentified

On the left side of the figure are the results for a sample containing 13% Fe. In contrast, the modeling results for the 0% Fe sample are shown in the right panel of the figure. In doing so, we can estimate the expected linear trend of each of the normalized axial ratios.

Figure 3.3: The normalized axial ratios are plotted in a purely geometric space against V −1/3 , where 13% Fe-bearing sample is on the left and the Fe-free sample on the right.
Figure 3.3: The normalized axial ratios are plotted in a purely geometric space against V −1/3 , where 13% Fe-bearing sample is on the left and the Fe-free sample on the right.

Obtaining Unbiased Estimates and Uncertainties for Equation of

In the absence of zero-pressure measurements of the sample volume, the correct way to constrain the parameter values ​​is to impose a reasonable composition-dependent assumption on V0. The one-dimensional marginal probability distributions for each parameter are shown on the edges of the figure. In addition, it is clear that the two different compositions have differences in their equations of state that are statistically discernible (though not necessarily all physically relevant, see discussion in Chapter 2), with little or no overlap in 2-D 95% confidence regions for any of the parameter pairs.

Figure 3.4: Examination of previous zero-pressure volume measurements as a function of iron content, using a linear fit combined with an intrinsic scatter due to sample-to-sample variation
Figure 3.4: Examination of previous zero-pressure volume measurements as a function of iron content, using a linear fit combined with an intrinsic scatter due to sample-to-sample variation

Conclusions

Second, and more important, is the fact that all previous investigations have determined a number of important equations of state parameters to improve apparent parameter constraints. We show how model parameters can be obtained by training on equation of state data for different crystal polymorphs that discretely sample the range of available coordination states. This method is applied to the MgO system and then used to calculate the coordination evolution and equation of state of liquid Mg over a wide range of pressures and temperatures.

Figure 3.5: Two-dimensional posterior plots show the correlations between the different equation of state parameter uncertainties
Figure 3.5: Two-dimensional posterior plots show the correlations between the different equation of state parameter uncertainties

Background

Ideal Mixing Models for Experimental Data

Given a measurement of fluid volumes and energies for a range of compositions at a particular P-T state, the ideal mixing model assumes that the volumes, entropies, and energies are additive and depend linearly on the fraction of each end-member composition. (Bottinga and Weill, 1970). Despite the widespread success, there are obvious shortcomings in the direct application of this approach, as explored by (Guo et al., 2013), in which they show evidence for large variations in the partial molar volume of the oxide component of of iron as a function of overall composition. Preliminary results from liquid shock wave experiments in the CaO−MgO−Al2O3−SiO2−FeO system show similar failures of the ideal mixture method (Thomas et al., submitted 2013), although it is not yet clear whether the practical approach of adding more end members that sample the range of dominant coordination states is sufficient to address the alignment deficiencies.

Atomic Simulation Using Molecular Dynamics

The major challenge with EPMD is related to the question of whether the parameter values ​​for the empirical potential are applicable outside the conditions under which they were trained and thus the quality of the simulation results can vary widely depending on the details of the system. First-Principles Molecular Dynamics (FPMD) avoids many of these issues surrounding accuracy of the applied forces by determining them directly using first-principles quantum mechanics calculations. Although this is likely to be sufficient for comparing state properties of most systems, any physical effects that rely on length scales approaching the size of the simulation cell will not be captured by this approach, making the determination of dynamic material properties such as diffusivity and viscosity difficult. make. possibly much more uncertain.

Basic Hard Sphere Model

The initial investigations of hard sphere fluids represent some of the first computer simulations ever performed. For moderate packing fractions (low density liquid phase), particles frequently interact with each other revealing the importance of the excluded volume. In the low density case, the particle can access almost the entire free volume of the liquid.

Figure 4.1: Snapshots of the simple hard sphere model for a range of packing fractions.
Figure 4.1: Snapshots of the simple hard sphere model for a range of packing fractions.

Previous Application of Hard Spheres to Silicate Liquids

This was achieved by determining a single effective hard sphere size for each fluid that best matched the 1 bar density measurement at the reference temperature. Recently, Jing and Karato (2011) made significant progress in describing hard sphere silicate melts by fitting a set of hard sphere diameters to a collection of liquid density measurements in the CaO–MgO–Al2O3–SiO2–FeO system. Initially, fixed diameters of hard spheres were found to best fit the liquid data in a least-squares fashion.

Local Liquid Structure

From this equation, it is clear that the radiation is scattered with high intensity only in a limited set of preferred directions that are characteristic of the crystal structure. Without going into details, we briefly mention some of the available techniques and the general knowledge they provide about high-pressure silicate melts. For visualization purposes, we reproduce a figure from Karki et al. 2007) shown in Figure 4.4, which shows the evolution of different Si−O coordination polyhedra with increasing compression.

Figure 4.3: Depiction of the radial distribution function (RDF) of a simple model liquid (in this case the Lennard-Jones fluid)
Figure 4.3: Depiction of the radial distribution function (RDF) of a simple model liquid (in this case the Lennard-Jones fluid)

Coordinated HArd Sphere Model (CHASM)

A Qualitative Picture of Liquid Compression

Including the dependence of the internal energy on the packing fraction results in a perturbed hard sphere model, where the sphere sizes adjust with compression. At the top left of the figure we start with the orderly compression of solids, which is dominated by changes in bond length. In the third panel we show how a more realistic fluid image causes the size of the hard sphere particles to change as a function of pressure (or temperature).

Figure 4.5: Compression mechanism cartoon for oxide liquids showing the different con- con-ceptual steps involved in getting from solid-like compression to liquid-like compression.
Figure 4.5: Compression mechanism cartoon for oxide liquids showing the different con- con-ceptual steps involved in getting from solid-like compression to liquid-like compression.

Perturbing the Hard Sphere Mixture Model

Therefore, the microstates of the system are populated in such a way as to minimize the total free energy. Together, the ideal and hard-sphere terms represent parts of the standard hard-sphere mixing model. Finally we come to the last term in the free energy expression, which captures the effects of the internal degrees of freedom of each particle of the hard sphere.

Training Pair Potentials on Solid Structures

This dependence is only important as a higher order correction to the free energy in terms of the bond angle contribution. Panel (a) shows the variation of the equilibrium radius, (b) shows the energy well depth and (c) shows the width of the energy well. Panels b and c show the variation of the energy well depth and width with coordination number.

Figure 4.6: Representation of the unit cell structures and oxygen coordination polyhedra for the six theoretically realizable polymorphs of MgO
Figure 4.6: Representation of the unit cell structures and oxygen coordination polyhedra for the six theoretically realizable polymorphs of MgO

Determining Liquid Properties using CHASM

The inset figure shows a zoomed-in view of the minimum, which occurs for a coordination number close to 6. In the previous section, we developed a simple polynomial description of the pair potential terms as a function of coordination number, as shown in Figure 4.8. Also, in the introduction of the same figure, the change of the defined diameters of the solid spheres with compression is presented.

Figure 4.10: Results from the pair potential global fit, showing the energy well correspond- correspond-ing to each fractional coordination number along a continuum between 3 and 10
Figure 4.10: Results from the pair potential global fit, showing the energy well correspond- correspond-ing to each fractional coordination number along a continuum between 3 and 10

Conclusions

All of these combine to express the contribution to the free energy and entropy e. Stixrude (2006), First-principles calculations of the structural, dynamical, and electronic properties of liquid MgO, Phys. Meng (2008), Effect of Fe on the equation of state of mantle silicate perovskite above 1Mbar, Earth Physics and Planetary Interiors.

Figure 4.13: Resulting equation of state curves for MgO liquid over a range of tempera- tempera-tures
Figure 4.13: Resulting equation of state curves for MgO liquid over a range of tempera- tempera-tures

Cold compression data map for 13% Fe-bearing perovskite

Cold compression data map for Mg-perovskite

Measured spectral temperatures for 13% Fe-bearing perovskite

Measured spectral temperatures for Mg-perovskite

Apparent deviatoric stress experienced by perovskite samples as determined

Cold compression curves with equation of state confidence regions for 0%

Excess volumes due to thermal expansion with best-fit isothermal equation

Joint confidence regions for core-mantle boundary volumes and bulk moduli

Normalized axial ratios and octahedral tilt angles for 0% and 13% Fe-bearing

Isothermal profiles with confidence regions for the physical properties of 0%

Buoyant stability of a perovskite-dominated LLSVP determined for a range

Compression evolution of peak positions for Mg-perovskite sample

Compression evolution of peak positions for 13% Fe-bearing perovskite sample 76

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