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

We investigated the stability of polymeric CO2 over a wide range of pressures, temperatures, and chemical environments. We find that the I-42d polymeric structure, consisting of a three-dimensional network of corner sharing CO4 tetrahedra, forms at 40-140 GPa and from a CO-N2 mixture at 39 GPa. An exceptional stability field of 0 to 286 GPa and 100 to 2500 K is documented for this structure, making it a viable candidate for planetary interiors. The stability of the tetrahedra...

The early Earth's environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically j...

We present a first principles molecular dynamics (FPMD) study of the interaction of low energy, positively charged, carbon (C+) projectiles with amorphous solid water clusters at 30 K. Reactions involving the carbon ion at an initial energy of 11 eV and 1.7 eV with 30-molecule clusters have been investigated. Simulations indicate that the neutral isoformyl radical, COH, and carbon monoxide, CO, are the dominant products of these reactions. All these reactions are accompanied ...

By employing $ab$ $initio$ molecular dynamics simulations at constant pressure, we investigated behavior of amorphous carbon dioxide between 0-100 GPa and 200-500 K and found several new amorphous forms. We focused on evolution of the high-pressure polymeric amorphous form known as a-carbonia on its way down to zero pressure, where it eventually converts into a molecular amorphous solid. During decompression, two nonmolecular amorphous forms with different proportion of three...

Understanding the co-evolution of complex life with Earth's geology is an enduring challenge. The rock record evidences remarkable correlations between changes in biology and the wider Earth system, yet cause and effect remain unclear. Here, we link the evolutionary history of eukaryotes with the rise and fall of carbonate rock fraction within continental crust - a key variable in controlling the efficiency of carbon drawdown during weathering, solid Earth degassing rates, an...

The climate of Mars likely evolved from a warmer, wetter early state to the cold, arid current state. However, no solutions for this evolution have previously been found to satisfy the observed geological features and isotopic measurements of the atmosphere. Here we show that a family of solutions exist, invoking no missing reservoirs or loss processes. Escape of carbon via CO photodissociation and sputtering enriches heavy carbon (13C) in the Martian atmosphere, partially co...

Carbon dioxide fixation and storage constitute a drastically important problem for the humanity nowadays. We hereby publish a new solution based on the alkaline earth salts with a weakly coordinating anion, tetrakis(pentafluorophenyl)borate. The proposed solution was validated using a robust combination of global minimum search and molecular dynamics simulations utilizing a well-tested, reliable semiempirical Hamiltonian to monitor chemical reactions. Calcium tetrakis(pentafl...

Water is an important component of exoplanets, with its distribution, i.e., whether at the surface or deep inside, fundamentally influencing the planetary properties. The distribution of water in most exoplanets is determined by yet-unknown partitioning coefficients at extreme conditions. Our new first-principles molecular dynamics simulations reveal that water strongly partitions into iron over silicate at high pressures and thus would preferentially stay in a planet's core....

There is a direct relation between the composition of a host star and that of the planets orbiting around it. As such, the recent discovery of stars with unusual chemical composition, notably enriched in carbon instead of oxygen, support the existence of exoplanets with a chemistry dominated by carbides instead of oxides. Accordingly several studies have been recently conducted on the Si C binary system at high pressure and temperature. Nonetheless, the properties of carbides...

Carbon capture and storage in basalt is being actively investigated as a scalable climate change mitigation option. Accurate geochemical modeling prediction of the extent and rate of CO2 mineralization is a critical component in assessing the local and global feasibility and efficacy of this strategy. In this study, we review basalt-CO2-water interaction experimental studies conducted during the last two decades to determine whether they provide useable information for geoche...