A many-body interatomic potential for ionic systems: application to MgO

An analytic representation of the short-range repulsion energy in ionic systems is described that allows for the fact that ions may change their size and shape depending on their environment. This function is extremely efficient to evaluate relative to previous methods of modeling the same physical effects. Using a well-defined parametrization procedure we have obtained parameter sets for this energy function that reproduce closely the density functional theory potential energy surface of bulk MgO. We show how excellent agreement can be obtained with experimental measurements of phonon frequencies and temperature and pressure dependences of the density by using this effective potential in conjunction with ab initio parametrization.Comment: To appear in Journal of Chemical Physics (Oct 15th 2003

First-principles thermoelasticity of bcc iron under pressure

We investigate the elastic and isotropic aggregate properties of ferromagnetic bcc iron as a function of temperature and pressure by computing the Helmholtz free energies for the volume-conserving strained structures using the first-principles linear response linear-muffin-tin-orbital method and the generalized-gradient approximation. We include the electronic excitation contributions to the free energy from the band structures, and phonon contributions from quasi-harmonic lattice dynamics. We make detailed comparisons between our calculated elastic moduli and their temperature and pressure dependences with available experimental and theoretical data.Comment: 5 figures, 2 table

Structures and stability of calcium and magnesium carbonates at mantle pressures

Ab initio random structure searching (AIRSS) and density functional theory methods are used to predict structures of calcium and magnesium carbonate (CaCO$_3$ and MgCO$_3$) at high pressures. We find a previously unknown CaCO$_3$ structure which is more stable than the aragonite and "post aragonite" phases in the range 32--48 GPa. At pressures from 67 GPa to well over 100 GPa the most stable phase is a previously unknown CaCO$_3$ structure of the pyroxene type with fourfold coordinated carbon atoms. We also predict a stable structure of MgCO$_3$ in the range 85--101 GPa. Our results lead to a revision of the phase diagram of CaCO$_3$ over more than half the pressure range encountered within the Earth's mantle, and smaller changes to the phase diagram of MgCO$_3$. We predict CaCO$_3$ to be more stable than MgCO$_3$ in the Earth's mantle above 100 GPa, and that CO$_2$ is not a thermodynamically stable compound under deep mantle conditions. Our results have significant implications for understanding the Earth's deep carbon cycle.We acknowledge financial support from the Engineering and Physical Sciences Research Council United Kingdom (EPSRC) of the United Kingdom.This is the author accepted manuscript. The final version is available from APS via http://dx.doi.org/10.1103/PhysRevB.91.10410

High-Temperature Thermodynamic Properties Of Forsterite

The high-temperature thermodynamic properties of forsterite were reviewed in the light of a new determination of the isobaric heat capacity (C(p)), up to 1850 K, and Raman spectroscopic measurements, up to 1150 K and 10 GPa. The C(p) measurements and available data on thermal expansion (alpha) and bulk modulus (K) show that the isochoric specific heat (C-nu) exceeds the harmonic limit of Dulong and Petit above 1300 K. This intrinsic anharmonic behavior of C-nu) can be modeled by introducing anharmonic parameters a(i) = (partial-lnv(i)/partial-T)V which are calculated from the measured pressure and temperature shifts of the vibrational frequencies. These parameters are all negative, with absolute values lower for the stretching modes of the SiO4 tetrahedra (a(i) almost-equal-to - 1 x 10(-5) K-1) than for the lattice modes (a(i) almost-equal-to 2 x 10(-5) K-1). Through the relation C(p) = C-nu) + alpha-2K(T)VT, the calculated anharmonic C-nu) and the measured C(p) are then used to determine the temperature dependences of the thermal expansion and bulk modulus of forsterite, up to 2000 K, in agreement with recent experimental results. Finally, all these data point to an inconsistency for the Gruneisen parameter of forsterite, whereby the macroscopic parameter gamma = alpha-VK(T)/C-nu) cannot be evaluated simply at high temperature by summation of the individual isothermal mode Gruneisen parameters gamma-iT = K(T) (partial-lnv(i)/partial-P)

quasiharmonic equations of state for dynamically-stabilized soft-mode materials

We introduce a method for treating soft modes within the analytical framework of the quasiharmonic equation of state. The corresponding double-well energy-displacement relation is fitted to a functional form that is harmonic in both the low- and high-energy limits. Using density-functional calculations and statistical physics, we apply the quasiharmonic methodology to solid periclase. We predict the existence of a B1--B2 phase transition at high pressures and temperatures

Theoretical and experimental evidence for a post-perovskite phase of MgSiO3 in Earth's D" layer

The Earth's lower mantle is believed to be composed mainly of (Mg,Fe)SiO3 perovskite, with lesser amounts of (Mg,Fe)O and CaSiO3). But it has not been possible to explain many unusual properties of the lowermost 150 km of the mantle (the D" layer) with this mineralogy. Here, using ab initio simulations and high-pressure experiments, we show that at pressures and temperatures of the D" layer, MgSiO3 transforms from perovskite into a layered CaIrO3-type post-perovskite phase. The elastic properties of the post-perovskite phase and its stability field explain several observed puzzling properties of the D" layer: its seismic anisotropy, the strongly undulating shear-wave discontinuity at its top and possibly the anticorrelation between shear and bulk sound velocities.Comment: PUBLISHED IN Nature 430, 445-448 (2004

Experimental investigation of the stability of Fe-rich carbonates in the lower mantle

International audienceThe fate of carbonates in the Earth's mantle plays a key role in the geodynamical carbon cycle. Although iron is a major component of the Earth's lower mantle, the stability of Fe-bearing carbonates has rarely been studied. Here we present experimental results on the stability of Fe-rich carbonates at pressures ranging from 40 to 105 GPa and temperatures of 1450-3600 K, corresponding to depths within the Earth's lower mantle of about 1000-2400 km. Samples of iron oxides and iron-magnesium oxides were loaded into CO2 gas and laser heated in a diamond-anvil cell. The nature of crystalline run products was determined in situ by X-ray diffraction, and the recovered samples were studied by analytical transmission electron microscopy and scanning transmission X-ray microscopy. We show that Fe-(II) is systematically involved in redox reactions with CO2 yielding to Fe-(III)-bearing phases and diamonds. We also report a new Fe-(III)-bearing high-pressure phase resulting from the transformation of FeCO3 at pressures exceeding 40 GPa. The presence of both diamonds and an oxidized C-bearing phase suggests that oxidized and reduced forms of carbon might coexist in the deep mantle. Finally, the observed reactions potentially provide a new mechanism for diamond formation at great depth

Thermodynamically Consistent Force Field for Molecular Dynamics Simulations of Alkaline-Earth Carbonates and Their Aqueous Speciation

In recent years atomistic simulations have become increasingly important in providing molecular insight to complement experiments. Even for the seemingly simple case of ion-pair formation a detailed atomistic picture of the structure and relative stability of the contact, solvent-shared and solvent-separated ion pairs can only be readily achieved by computer simulation. Here a new force field parametrization for the alkaline-earth carbonate interactions in water has been developed by fitting against experimental thermodynamic and structural data. We demonstrate that the present force field can accurately reproduce the dynamics and thermodynamics of the ions in solution, which is the key to producing quantitatively accurate data that can be compared against experiment

Composition of the Earth's Inner Core from High-pressure Sound Velocity Measurements in Fe-Ni-Si alloys

International audienceWe performed room-temperature sound velocity and density measurements on a polycrystalline alloy, Fe0.89Ni0.04Si0.07, in the hexagonal close-packed (hcp) phase up to 108 GPa. Over the investigated pressure range the aggregate compressional sound velocity is ∼9% higher than in pure iron at the same density. The measured aggregate compressional (VP) and shear (VS) sound velocities, extrapolated to core densities and corrected for anharmonic temperature effects, are compared with seismic profiles. Our results provide constraints on the silicon abundance in the core, suggesting a model that simultaneously matches the primary seismic observables, density, P-wave and S-wave velocities, for an inner core containing 4 to 5 wt.% of Ni and 1 to 2 wt.% of Si

Outcome of alimentary tract duplications operated on by minimally invasive surgery: a retrospective multicenter study by the GECI (Groupe d'Etude en Coeliochirurgie Infantile).

BACKGROUND: Alimentary tract duplications (ATD) are a rare cause of intestinal obstruction in childhood. There are many case reports but few series about laparoscopy or thoracoscopy for ATD. The aim of our study was to report the outcome of minimally invasive surgery (MIS) for ATD. METHODS: This was a retrospective multicenter study from the GECI (Groupe d\u27Etude en Coeliochirurgie Infantile). We reviewed the charts of 114 patients operated on by MIS for ATD from 1994 to 2009. RESULTS: Sixty-two patients (54 %) had a prenatal diagnosis. Forty-nine patients (43 %) were symptomatic before surgery: 33 of those patients (63 %) with postnatal diagnosis compared to 16 (25 %) with prenatal diagnosis (P < 0.01). In this last group, the median age at onset of symptoms was 16 days (range = 0-972). One hundred and two patients had laparoscopy (esophageal to rectal duplications) and 12 patients had thoracoscopy for esophageal duplications. The mean operative time was 90 min (range = 82-98). There were 32 (28 %) resection anastomoses, 55 (48 %) enucleations, and 27 (24 %) unroofings. The conversion rate was 32 %, and in a multivariate analysis, it was significantly higher, up to 41 % for patients weighing <10 kg (P < 0.01). Ten patients (8 %) had unintentional perioperative opening of the digestive tract during the dissection. Eight patients had nine postoperative complications, including six small bowel obstructions. The median length of hospital stay was 4 days (range = 1-21) without conversion and 6 days (range = 1-27) with conversion (P = 0.01). The median follow-up was 3 months (range = 1-120). Eighteen of the 27 patients who underwent partial surgery had an ultrasound examination during follow-up. Five (18 %) of them had macroscopic residue. CONCLUSION: This study showed that MIS for ATD is feasible with a low rate of complications. Patients with prenatal diagnosis should have prompt surgery to prevent symptoms, despite a high rate of conversion in small infants