Raman spectroscopy and X-ray diffraction of sp3-CaCO3 at lower mantle pressures

The melting curve and fluid equation of state of carbon dioxide have been determined under high pressure in a resistively-heated diamond anvil cell. The melting line was determined from room temperature up to $11.1\pm0.1$ GPa and $800\pm5$ K by visual observation of the solid-fluid equilibrium and in-situ measurements of pressure and temperature. Raman spectroscopy was used to identify the solid phase in equilibrium with the melt, showing that solid I is the stable phase alon...

Search of materials with C-N composition hold a great promise in creating materials which would rival diamond in hardness due to the very strong and relatively low-ionic C-N bond. Early experimental and theoretical works on C-N compounds were based on structural similarity with binary A3B4 structural- types; however, the synthesis of C3N4 remains elusive. Here we explored an unbiased synthesis from the elemental materials at high pressures and temperatures. Using in situ sync...

The observed "simple cubic" (sc) phase of elemental Ca at room temperature in the 32-109 GPa range is, from linear response calculations, dynamically unstable. By comparing first principle calculations of the enthalpy for five sc-related (non-close-packed) structures, we find that all five structures compete energetically at room temperature in the 40-90 GPa range, and three do so in the 100-130 GPa range. Some competing structures below 90 GPa are dynamically stable, i.e., n...

The physicochemical behavior of elements and compounds is heavily altered by high pressure. The occurrence of pressure-induced reactions and phase transitions can be revealed by crystal structure prediction approaches. In this work, we explore the C-H-O phase diagram up to 400 GPa exploiting an evolutionary algorithm for crystal structure predictions along with ab initio calculations. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we p...

We report on a high-pressure Raman study on two members of the La$_{1-x}$Ca$_x$MnO$_{3-\delta}$ manganite family ($x=0.20$, $\delta=0$ and $\delta=0.08$). The results obtained for the $\delta=0$ sample show a different behavior in the low and high pressure regimes ascribed to the onset of a new pressure-activated interaction previously invoked in other manganite compounds. The comparison of our results with literature data gives further support to the identification of the Ja...

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...

Ferromagnesite (Mg,Fe)CO3, also referred to as magnesiosiderite at high iron concentration, is a solid solution of magnesite (MgCO3) and siderite (FeCO3). Ferromagnesite is believed to enter the Earth's lower mantle via subduction and is considered a major carbon carrier in the Earth's lower mantle, playing a key role in the Earth's deep carbon cycle. Experiments have shown that ferromagnesite undergoes a pressure-induced spin crossover, accompanied by volume and elastic anom...

The pressure influence on the lattice vibration of $CaZnF_4$ has been studied by Raman diffusion up to 17 GPa. Most Raman frequencies increase with increasing pressure. Three singularities in the pressure induced frequency evolution are observed around 1.5 GPa, 10 GPa and 17 GPa. The samples pressurized to 17 GPa or higher do not revert to the ambient pressure phase after being released, the new phase showing different Raman spectra from the ordinary one. It is suggested that...

Ternary C_{x}N_{y}O_{z} compounds are actively researched as novel high energy density and ultrahard materials. Although some synthesis work has been performed at ambient conditions, very little is known about the high pressure chemistry of of C_{x}N_{y}O_{z} compounds. In this work, first principles variable-composition evolutionary structure prediction calculations are performed with the goal of discovering novel mixed C_{x}N_{y}O_{z} materials at ambient and high pressure ...

Synchrotron X-ray powder diffraction experiments reveal that the transition from a magnetic intermediate spin (IS) state to a nonmagnetic low-spin (LS) ground state in LaCoO3 normally observed when cooling, manifests itself under pressure by an anomalously low bulk compressibility of 150(2) GPa and an initially very large bond compressibility of 4.8e-3 GPa-1 which levels off near 4 GPa. The continuous depopulation of the IS state is driven by an increased crystal field splitt...