Structure, Bonding, and Mineralogy of Carbon at Extreme Conditions

The nature and extent of Earth’s deep carbon cycle remains uncertain. This chapter considers high-pressure carbon-bearing minerals, including those of Earth’s mantle and core, as well as phases that might be found in the interiors of larger planets outside our solar system. These phases include both experimentally produced and theoretically predicted polymorphs of carbon dioxide, carbonates, carbides, silicate-carbonates, as well as very high-pressure phases of pure carbon. One theme in the search for possible high P-T, deep-Earth phases is the likely shift from sp2 bonding (trigonal coordination) to sp3 bonding (tetrahedral coordination) in carbon-bearing phases of the lower mantle and core, as exemplified by the graphite-to-diamond transition (Bundy et al. 1961; Davies 1984). A similar phenomenon has been documented in the preferred coordination spheres of many elements at high pressure. For example, silicon is ubiquitously found in tetrahedral coordination in crustal and upper mantle minerals, but adopts octahedral coordination in many high-pressure phases. Indeed, the boundary between Earth’s transition zone and lower mantle may be described as a crystal chemical shift from 4-coordinated to 6-coordinated silicon (Hazen and Finger 1978; Finger and Hazen 1991). Similarly, magnesium and calcium commonly occur in octahedral 6-coordination in minerals at ambient conditions, but transform to 8- or greater coordination in high-pressure phases, as exemplified by the calcite-to-aragonite transformation of CaCO3 and the pyroxene-to-perovskite and post-perovskite transformations of MgSiO3 (Murakami et al. 2004; Oganov and Ono 2004). Consequently, a principal focus in any consideration of deep-Earth carbon minerals must include carbon in higher coordination, and even more complex bonding at more extreme conditions that characterize the interiors of larger planets

A quantum fluid of metallic hydrogen suggested by first-principles calculations

It is generally assumed that solid hydrogen will transform into a metallic alkali-like crystal at sufficiently high pressure. However, some theoretical models have also suggested that compressed hydrogen may form an unusual two-component (protons and electrons) metallic fluid at low temperature, or possibly even a zero-temperature liquid ground state. The existence of these new states of matter is conditional on the presence of a maximum in the melting temperature versus pressure curve (the 'melt line'). Previous measurements of the hydrogen melt line up to pressures of 44 GPa have led to controversial conclusions regarding the existence of this maximum. Here we report ab initio calculations that establish the melt line up to 200 GPa. We predict that subtle changes in the intermolecular interactions lead to a decline of the melt line above 90 GPa. The implication is that as solid molecular hydrogen is compressed, it transforms into a low-temperature quantum fluid before becoming a monatomic crystal. The emerging low-temperature phase diagram of hydrogen and its isotopes bears analogies with the familiar phases of 3He and 4He, the only known zero-temperature liquids, but the long-range Coulombic interactions and the large component mass ratio present in hydrogen would ensure dramatically different propertiesComment: See related paper: cond-mat/041040

A superconductor to superfluid phase transition in liquid metallic hydrogen

Although hydrogen is the simplest of atoms, it does not form the simplest of solids or liquids. Quantum effects in these phases are considerable (a consequence of the light proton mass) and they have a demonstrable and often puzzling influence on many physical properties, including spatial order. To date, the structure of dense hydrogen remains experimentally elusive. Recent studies of the melting curve of hydrogen indicate that at high (but experimentally accessible) pressures, compressed hydrogen will adopt a liquid state, even at low temperatures. In reaching this phase, hydrogen is also projected to pass through an insulator-to-metal transition. This raises the possibility of new state of matter: a near ground-state liquid metal, and its ordered states in the quantum domain. Ordered quantum fluids are traditionally categorized as superconductors or superfluids; these respective systems feature dissipationless electrical currents or mass flow. Here we report an analysis based on topological arguments of the projected phase of liquid metallic hydrogen, finding that it may represent a new type of ordered quantum fluid. Specifically, we show that liquid metallic hydrogen cannot be categorized exclusively as a superconductor or superfluid. We predict that, in the presence of a magnetic field, liquid metallic hydrogen will exhibit several phase transitions to ordered states, ranging from superconductors to superfluids.Comment: for a related paper see cond-mat/0410425. A correction to the front page caption appeared in Oct 14 issue of Nature: http://www.nature.com/nature/links/041014/041014-11.htm

Transformation Pathways of Silica under High Pressure

Concurrent molecular dynamics simulations and ab initio calculations show that densification of silica under pressure follows a ubiquitous two-stage mechanism. First, anions form a close-packed sub-lattice, governed by the strong repulsion between them. Next, cations redistribute onto the interstices. In cristobalite silica, the first stage is manifest by the formation of a metastable phase, which was observed experimentally a decade ago, but never indexed due to ambiguous diffraction patterns. Our simulations conclusively reveal its structure and its role in the densification of silica.Comment: 14 pages, 4 figure

Understanding high pressure hydrogen with a hierarchical machine-learned potential

The hydrogen phase diagram has a number of unusual features which are generally well reproduced by density functional calculations. Unfortunately, these calculations fail to provide good physical insights into why those features occur. In this paper, we parameterize a model potential for molecular hydrogen which permits long and large simulations. The model shows excellent reproduction of the phase diagram, including the broken-symmetry Phase II, an efficiently-packed phase III and the maximum in the melt curve. It also gives an excellent reproduction of the vibrational frequencies, including the maximum in the vibrational frequency $\nu(P)$ and negative thermal expansion. By detailed study of lengthy molecular dynamics, we give intuitive explanations for observed and calculated properties. All solid structures approximate to hexagonal close packed, with symmetry broken by molecular orientation. At high pressure, Phase I shows significant short-ranged correlations between molecular orientations. The turnover in Raman frequency is due to increased coupling between neighboring molecules, rather than weakening of the bond. The liquid is denser than the close-packed solid because, at molecular separations below 2.3\AA, the favoured relative orientation switches from quadrupole-energy-minimising to steric-repulsion-minimising. The latter allows molecules to get closer together, without atoms getting closer but this cannot be achieved within the constraints of a close-packed layer

The self-organizing fractal theory as a universal discovery method: the phenomenon of life

A universal discovery method potentially applicable to all disciplines studying organizational phenomena has been developed. This method takes advantage of a new form of global symmetry, namely, scale-invariance of self-organizational dynamics of energy/matter at all levels of organizational hierarchy, from elementary particles through cells and organisms to the Universe as a whole. The method is based on an alternative conceptualization of physical reality postulating that the energy/matter comprising the Universe is far from equilibrium, that it exists as a flow, and that it develops via self-organization in accordance with the empirical laws of nonequilibrium thermodynamics. It is postulated that the energy/matter flowing through and comprising the Universe evolves as a multiscale, self-similar structure-process, i.e., as a self-organizing fractal. This means that certain organizational structures and processes are scale-invariant and are reproduced at all levels of the organizational hierarchy. Being a form of symmetry, scale-invariance naturally lends itself to a new discovery method that allows for the deduction of missing information by comparing scale-invariant organizational patterns across different levels of the organizational hierarchy

Elasticity and rheology of iron above 220 GPa and the nature of the Earth's inner core

Recent numerical-modelling and seismological results have raised new questions about the dynamics` - ' and magnetism of the Earth's core. Knowledge of the elasticity and texture of irons' ' at core pressures is crucial for understanding the seismological ; observations, such as the low attenuation of seismic waves, the low shear-wave velocity and the anisotropy of compressional-wave velocity - quot;. The density and bulk modulus of hexagonal-close-packed iron have been previously measured to 1 core pressures by staticquot; and dynamicquot;,quot; methods. Here we study, using radial X-ray diffraction 1 5 and ultrasonic techniques', I the shear modulus, single-crystal elasticity tensor, aggregate compressional- and shear-wave velocities, and orientation dependents of these velocities in iron. The inner core shear-wave velocity is lower than the aggregate shear-wave velocity of iron, suggesting the presence of low-velocity components or anelastic effects in the core. Observation of a strong lattice strain anisotropy in iron samples indicates a large (--24% compressional wave anisotropy under the isostress assumption, and therefore a perfect alignment of crystals, would not be needed to explain the seismic observations. Alternatively the strain anisotropy may indicate stress variation due to preferred slip systems

Estimation of single-crystal elastic moduli from polycrystalline x-ray diffraction at high pressure: application to FeO and Iron

X-ray diffraction data obtained under nonhydrostatic compression of a polycrystalline sample yield13; an estimate of the single-crystal elasticity tensor of the material when analyzed using appropriate13; equations. The analysis requires as input the aggregate shear modulus from independent measurements.13; The high-pressure elastic moduli of face-centered-cubic FeO, body-centered-cubic iron (a-Fe), and the13; pressure-induced hexagonal close-packed iron (e-Fe) are obtained. This analysis currently provides13; the only method of determining single-crystal elasticity tensors in the megabar pressure range and of13; studying elasticity of very high-pressure phases

Analysis of lattice strains measured under nonhydrostatic pressure13;

The equations for the lattice strains produced by nonhydrostatic compression are presented for all seven crystal systems in a form convenient for analyzing x-ray diffraction data obtained by newly developed methods. The equations have been used to analyze the data on cubic (hec a-Fe) and hexagonal (hop E-Fe)system. The analysis gives information on the strain produced by the hydrostatic stress component. A new method of estimating the uniaxial stress component from diffraction data is presented. Most importantly, the present analysis provides a general method of determining single crystal elastic constants of ultrahigh pressures

Strength, Anisotropy, and preferred orientation of solid13; argon at high pressures

The elasticity and plasticity of materials at high pressure are of great importance for the fundamental insight they provide on bonding properties in dense matter and for applications ranging from geophysics to materials technology. We studied pressure-solidified argon with a boronx2013;epoxyx2013;beryllium composite gasket in a diamond anvil cell (DAC). Employing monochromatic synchrotron13; x-radiation and imaging plates in a radial diffraction geometry (Singh et al 1998 Phys. Rev. Lett. 80 2157; Mao et al 1998 Nature 396 741), we observed low strength in solid argon below 20 GPa, but the strength increases drastically with applied pressure, such that at 55 GPa, the shear strength exceeded 2.7 GPa. The elastic anisotropy at 55 GPa was four times higher than the extrapolated value from 30 GPa. Extensive (111) slip develops under uniaxial compression, as manifested by the preferred crystallographic orientation of (220) in the compression direction. These macroscopic properties reflect basic changes in van der Waals bondings under ultra high pressures