Carbon Dioxide, Bicarbonate and Carbonate Ions in Aqueous Solutions at Deep Earth Conditions

Carbon, the fourth most abundant element in the Universe forms a metallic fluid with transient covalent bonds on melting. Its liquid-liquid phase transitions, intensely sought using simulations had been elusive. Here we use density functional theory (DFT) simulations with up to 108 atoms using molecular dynamics, as well as one-atom DFT as implemented in the neutral pseudo-atom method where multi-atom effects are treated by ion-ion correlation functionals. Both methods use el...

In this work, the effects of finite size on the determination of the three-phase coexistence temperature ($T_3$) of carbon dioxide (CO$_2$) hydrate have been studied by molecular dynamic simulations and using the direct coexistence technique. According to this technique, the three phases involved are placed together in the same simulation box. By varying the number of molecules of each phase it is possible to analyze the effect of simulation size and stoichiometry on the $T_3...

The amount of H$_2$O and CO$_2$ that is carried into deep mantle by subduction beyond subarc depths is of fundamental importance to the deep volatile cycle but remains debated. Given the large uncertainties surrounding the spatio-temporal pattern of fluid flow and the equilibrium state within subducting slabs, a model of H$_2$O and CO$_2$ transport in slabs should be balanced between model simplicity and capability. We construct such a model in a two-part contribution. In thi...

Accurate prediction of a gas solubility in a liquid is crucial in many areas of chemistry, and a detailed understanding of the molecular mechanism of the gas solvation continues to be an active area of research. Here, we extend the idea of constant chemical potential molecular dynamics (C{\mu}MD) approach to the calculation of the gas solubility in the liquid under constant gas chemical potential conditions. As a representative example, we utilize this method to calculate the...

Although they are rare elements in the Earth's mantle, noble gases (NG) owe to their strongly varying masses contrasting physical behaviors making them important geochemical tracers. When partial melting occurs at depth, the partitioning of NGs between phases is controlled by a distribution coefficient that can be determined from the solubility of the NGs in each phase. Here we report quantitative calculations of the solubility of He, Ne, Ar and Xe in carbonate melts based on...

We present a 5-phase equation of state (EOS) for elemental carbon. The phases considered are: diamond, BC8, simple-cubic, simple-hexagonal, and the liquid/plasma state. The solid phase free energies are constrained by density functional theory (DFT) calculations. Vibrational contributions to the free energy of each solid phase are treated within the quasiharmonic framework. The liquid free energy model is constrained by fitting to a combination of DFT molecular dynamics perfo...

Molecular dynamics simulations using classical force fields were carried out to study energetic and structural properties of rotationally disordered clay mineral-water-CO2 systems at pressure and temperature relevant to geological carbon storage. The simulations show that turbostratic stacking of hydrated Na- and Ca-montmorillonite and hydrated montmorillonite with intercalated carbon dioxide is an energetically demanding process accompanied by an increase in the interlayer s...

Based on a pressure-temperature (P-T) phase diagram model of the Earth, Jones & Lineweaver (2010) described uninhabited terrestrial liquid water. Our model represents the atmosphere, surface, oceans and interior of the Earth - allowing the range of P-T conditions in terrestrial environments to be compared to the phase regime of liquid water. Here we present an overview and additional results from the Earth model on the location of the deepest liquid water on Earth and the max...

The exceptional ability of carbon to form sp2 and sp3 bonding states leads to a great structural and chemical diversity of carbon-bearing phases at non-ambient conditions. Here we use laser-heated diamond anvil cells combined with synchrotron x-ray diffraction, Raman spectroscopy, and first-principles calculations to explore phase transitions in CaCO3 at P > 40 GPa. We find that post-aragonite CaCO3 transforms to the previously predicted P21/c-CaCO3 with sp3-hybridized carbon...

The proportions of oxygen, carbon and major rock-forming elements (e.g. Mg, Fe, Si) determine a planet's dominant mineralogy. Variation in a planet's mineralogy subsequently affects planetary mantle dynamics as well as any deep water or carbon cycle. Through thermodynamic models and high pressure diamond anvil cell experiments, we demonstrate the oxidation potential of C is above that of Fe at all pressures and temperatures indicative of 0.1 - 2 Earth-mass planets. This means...