analyzing-melts-fluids-from-ab-initio-molecular-dynamics-simulations

Analyzing Melts and Fluids from Ab Initio Molecular Dynamics Simulations with the UMD Package

We have developed a Python-based open-source package to analyze the results stemming from ab initio molecular-dynamics simulations of fluids. The package ...

CNRS

University of Oslo

Water ice X is stable in the 120-400 GPa pressure range, as obtained from lattice dynamical calculations performed using the density-functional theory. Below 120 GPa, it is characterized by one unstable flat phonon band, which generates the disordered ice X structure. Above 400 GPa, ice X has an unstable phonon mode in M, which leads to the Pbcm orthorhombic structure obtained in previous molecular-dynamics calculations [M. Benoit, M. Bernasconi, P. Focher, and M. Parrinello, Phys. Rev. Lett. 76, 2934 (1996)10.1103/PhysRevLett.76.2934]. Therefore, based on lattice dynamics, we propose that the high-pressure low-temperature phase-transition sequence in H2O ice is ice VIII-disordered ice X-ordered ice X-ice Pbcm.

Dynamical instabilities of ice X.

The origin of longstanding anomalies in experimental studies of the dense solid phases of H2O ices VII, VIII, and X is examined using a combination of first-principles theoretical methods. We find that a ferroelectric variant of ice VIII is energetically competitive with the established antiferroelectric form under pressure. The existence of domains of the ferroelectric form within anti-ferroelectric ice can explain previously observed splittings in x-ray diffraction data. The ferroelectric form is stabilized by density and is accompanied by the onset of spontaneous polarization. The presence of local electric fields triggers the preferential parallel orientation of the water molecules in the structure, which could be stabilized in bulk using new high-pressure techniques. 

Ferroelectricity in high-density H2O ice.

From first-principles molecular dynamics, we investigate the relation between the superionic proton conduction and the behavior of the O─H⋯O bond (ice VII^{'} to ice X transition) in body-centered-cubic (bcc) H_{2}O ice between 1300 and 2000 K and up to 300 GPa. We bring evidence that there are three distinct phases in the superionic bcc stability field. A first superionic phase characterized by extremely fast diffusion of highly delocalized protons (denoted VII^{''}  hereinafter) is stable at low pressures. A first-order transition separates this phase from a superionic VII^{'}, characterized by a finite degree of localization of protons along the nonsymmetric O─H⋯O bonds. The transition is identified in structural, energetic, and elastic analysis. Upon further compression a second-order phase transition leads to the superionic ice X with symmetric O─H─O bonds.

Superionic-Superionic Phase Transitions in Body-Centered Cubic H_{2}O Ice.

In various shocked meteorites, low-pressure silica polymorph α-cristobalite is commonly found in close spatial relation with the densest known SiO polymorph seifertite, which is stable above ∼80 GPa. We demonstrate that under hydrostatic pressure α-cristobalite remains untransformed up to at least 15 GPa. In quasi-hydrostatic experiments, above 11 GPa cristobalite X-I forms-a monoclinic polymorph built out of silicon octahedra; the phase is not quenchable and back-transforms to α-cristobalite on decompression. There are no other known silica polymorphs, which transform to an octahedra-based structure at such low pressures upon compression at room temperature. Further compression in non-hydrostatic conditions of cristobalite X-I eventually leads to the formation of quenchable seifertite-like phase. Our results demonstrate that the presence of α-cristobalite in shocked meteorites or rocks does not exclude that materials experienced high pressure, nor is the presence of seifertite necessarily indicative of extremely high peak shock pressures.

Compressional pathways of α-cristobalite, structure of cristobalite X-I, and towards the understanding of seifertite formation.

Current estimates of the carbon flux between the surface and mantle are highly variable, and the total amount of carbon stored in closed hidden reservoirs is unknown. Understanding the forms in which carbon existed in the molten early Earth is a critical step towards quantifying the carbon budget of Earth's deep interior. Here we employ first-principles molecular dynamics to study the evolution of carbon species as a function of pressure in a pyrolite melt. We find that with increasing pressure, the abundance of CO and CO species decreases at the expense of CO and complex oxo-carbon polymers (CO) displaying multiple C-C bonds. We anticipate that polymerized oxo-carbon species were a significant reservoir for carbon in the terrestrial magma ocean. The presence of Fe-C clusters suggests that upon segregation, Fe-rich metal may partition a significant fraction of carbon from the silicate liquid, leading to carbon transport into the Earth's core.

Carbon sequestration during core formation implied by complex carbon polymerization.

The position of the vapor-liquid dome and of the critical point determine the evolution of the outermost parts of the protolunar disk during cooling and condensation after the Giant Impact. The parts of the disk in supercritical or liquid state evolve as a single thermodynamic phase; when the thermal trajectory of the disk reaches the liquid-vapor dome, gas and melt separate leading to heterogeneous convection and phase separation due to friction. Different layers of the proto-Earth behaved differently during the Giant Impact depending on their constituent materials and initial thermodynamic conditions. Here we use first-principles molecular dynamics to determine the position of the critical point for NaAlSiO and KAlSiO feldspars, major minerals of the Earth and Moon crusts. The variations of the pressure calculated at various volumes along isotherms yield the position of the critical points: 0.5-0.8 g cm and 5500-6000 K range for the Na-feldspar, 0.5-0.9 g cm and 5000-5500 K range for the K-feldspar. The simulations suggest that the vaporization is incongruent, with a degassing of O starting at 4000 K and gas component made mostly of free Na and K cations, O, SiO and SiO species for densities below 1.5 g cm. The Hugoniot equations of state imply that low-velocity impactors (<8.3 km s) would at most melt a cold feldspathic crust, whereas large impacts in molten crust would see temperatures raise up to 30000 K.

The Critical Point and the Supercritical State of Alkali Feldspars: Implications for the Behavior of the Crust During Impacts.

The ab initio (ai) Gibbs ensemble (GE) Monte Carlo (MC) method coupled with Kohn-Sham density functional theory is successful in predicting the liquid-vapour equilibrium of insulating systems. Here we show that the aiGEMC method can be used to study also metallic systems, where the excited electronic states play an important role and cannot be neglected. For this we include the electronic free energy in the formulation of the effective energy of the system to be used in the acceptance criteria for the MC moves. The application of this aiGEMC method to sodium yields a good agreement with available experimental data on the liquid-vapour equilibrium densities. We predict a critical point for sodium at 2338 ± 108 K and 0.24 ± 0.03 g cm-3. The liquid structure stemming from aiGEMC simulations is very similar to the one from ab initio molecular dynamics. Since this method can determine phase transition without computing the Gibbs free energy, it may offer a new possibility to study other materials with a reasonable computational cost.

 Gibbs ensemble Monte Carlo simulations of the liquid-vapor equilibrium and the critical point of sodium.

The early Earth was marked by at least one global magma ocean. Melt buoyancy played a major role for its evolution. Here we model the composition of the magma ocean using a six-component pyrolite melt, to which we add volatiles in the form of carbon as molecular CO or CO and hydrogen as molecular HO or through substitution for magnesium. We compute the density relations from first-principles molecular dynamics simulations. We find that the addition of volatiles renders all the melts more buoyant compared to the reference volatile-free pyrolite. The effect is pressure dependent, largest at the surface, decreasing to about 20 GPa, and remaining roughly constant to 135 GPa. The increased buoyancy would have enhanced convection and turbulence, and thus promoted the chemical exchanges of the magma ocean with the early atmosphere. We determine the partial molar volume of both HO and CO throughout the magma ocean conditions. We find a pronounced dependence with temperature at low pressures, whereas at megabar pressures the partial molar volumes are independent of temperature. At all pressures, the polymerization of the silicate melt is strongly affected by the amount of oxygen added to the system while being only weakly affected by the specific type of volatile added.

Article	Year
Dynamical instabilities of ice X. Physical review letters\| PubMed ID: 18764633	2008
Ferroelectricity in high-density H2O ice. The Journal of chemical physics\| PubMed ID: 25854247	2015
Superionic-Superionic Phase Transitions in Body-Centered Cubic H_{2}O Ice. Physical review letters\| PubMed ID: 27715129	2016
Compressional pathways of α-cristobalite, structure of cristobalite X-I, and towards the understanding of seifertite formation. Nature communications\| PubMed ID: 28589935	2017
Carbon sequestration during core formation implied by complex carbon polymerization. Nature communications\| PubMed ID: 30770828	2019
The Critical Point and the Supercritical State of Alkali Feldspars: Implications for the Behavior of the Crust During Impacts. Journal of geophysical research. Planets\| PubMed ID: 33133994	2020
Gibbs ensemble Monte Carlo simulations of the liquid-vapor equilibrium and the critical point of sodium. Physical chemistry chemical physics : PCCP\| PubMed ID: 33347522	2021
Buoyancy and Structure of Volatile-Rich Silicate Melts. Journal of geophysical research. Solid earth\| PubMed ID: 33680690	2021

Razvan Caracas

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