Hexagonal structure of phase III of solid hydrogen

A hexagonal structure of solid molecular hydrogen with $P6_122$ symmetry is calculated to be more stable below about 200 GPa than the monoclinic $C2/c$ structure identified previously as the best candidate for phase III. We find that the effects of nuclear quantum and thermal vibrations play a central role in the stabilization of $P6_122$. The $P6_122$ and $C2/c$ structures are very similar and their Raman and infra-red data are in good agreement with experiment. However, our calculations show that the hexagonal $P6_122$ structure provides better agreement with the available x-ray diffraction data than the $C2/c$ structure at pressures below about 200 GPa. We suggest that two phase-III-like structures may be formed at high pressures, hexagonal $P6_122$ below about 200 GPa and monoclinic $C2/c$ at higher pressures.B.M. acknowledges Robinson College, Cambridge, and the Cambridge Philosophical Society for a Henslow Research Fellowship. R.J.N., E.G., and C.J.P. acknowledge financial support from the Engineering and Physical Sciences Research Council (EPSRC) of the United Kingdom (Grants No. EP/J017639/1, No. EP/J003999/1, and No. EP/K013688/1, respectively). C.J.P. is also supported by the Royal Society through a Royal Society Wolfson Research Merit award. The calculations were performed on the Darwin Supercomputer of the University of Cambridge High Performance Computing Service facility (http://www.hpc.cam.ac.uk/) and the Archer facility of the UK national high performance computing service, for which access was obtained via the UKCP consortium and funded by EPSRC Grant No. EP/K014560/1.This is the author accepted manuscript. The final version is available from the American Physical Society via https://doi.org/10.1103/PhysRevB.94.13410

The Interiors of Giant Planets: Models and Outstanding Questions

We know that giant planets played a crucial role in the making of our Solar System. The discovery of giant planets orbiting other stars is a formidable opportunity to learn more about these objects, what is their composition, how various processes influence their structure and evolution, and most importantly how they form. Jupiter, Saturn, Uranus and Neptune can be studied in detail, mostly from close spacecraft flybys. We can infer that they are all enriched in heavy elements compared to the Sun, with the relative global enrichments increasing with distance to the Sun. We can also infer that they possess dense cores of varied masses. The intercomparison of presently caracterised extrasolar giant planets show that they are also mainly made of hydrogen and helium, but that they either have significantly different amounts of heavy elements, or have had different orbital evolutions, or both. Hence, many questions remain and are to be answered for significant progresses on the origins of planets.Comment: 43 pages, 11 figures, 3 tables. To appear in Annual Review of Earth and Planetary Sciences, vol 33, (2005

Thermal equation of state of cubic boron nitride: Implications for a high-temperature pressure scale

The equation of state of cubic boron nitride (cBN) has been determined to a maximum temperature of 3300 K at a simultaneous static pressure of up to more than 70 GPa. Ab initio calculations to 80 GPa and 2000 K have also been performed. Our experimental data can be reconciled with theoretical results and with the known thermal expansion at 1 bar if we assume a small increase in pressure during heating relative to that measured at ambient temperature. The present data combined with the Raman measurements we presented earlier form the basis of a high-temperature pressure scale that is good to at least 3300 K

Transparent dense sodium

Under pressure, metals exhibit increasingly shorter interatomic distances. Intuitively, this response is expected to be accompanied by an increase in the widths of the valence and conduction bands and hence a more pronounced free-electron-like behaviour. But at the densities that can now be achieved experimentally, compression can be so substantial that core electrons overlap. This effect dramatically alters electronic properties from those typically associated with simple free-electron metals such as lithium and sodium, leading in turn to structurally complex phases and superconductivity with a high critical temperature. But the most intriguing prediction - that the seemingly simple metals Li and Na will transform under pressure into insulating states, owing to pairing of alkali atoms - has yet to be experimentally confirmed. Here we report experimental observations of a pressure-induced transformation of Na into an optically transparent phase at 200 GPa (corresponding to 5.0-fold compression). Experimental and computational data identify the new phase as a wide bandgap dielectric with a six-coordinated, highly distorted double-hexagonal close-packed structure. We attribute the emergence of this dense insulating state not to atom pairing, but to p-d hybridizations of valence electrons and their repulsion by core electrons into the lattice interstices. We expect that such insulating states may also form in other elements and compounds when compression is sufficiently strong that atomic cores start to overlap strongly.Comment: Published in Nature 458, 182-185 (2009

High-pressure polymorphism in pyridine

Single crystals of the high-pressure phases II and III of pyridine have been obtained by in situ crystallization at 1.09 and 1.69 GPa, revealing the crystal structure of phase III for the first time using X-ray diffraction. Phase II crystallizes in P212121 with Z' = 1 and phase III in P41212 with Z' = ½. Neutron powder diffraction experiments using pyridine-d5 establish approximate equations of state of both phases. The space group and unit-cell dimensions of phase III are similar to the structures of other simple compounds with C 2v molecular symmetry, and the phase becomes stable at high pressure because it is topologically close-packed, resulting in a lower molar volume than the topologically body-centred cubic phase II. Phases II and III have been observed previously by Raman spectroscopy, but have been mis-identified or inconsistently named. Raman spectra collected on the same samples as used in the X-ray experiments establish the vibrational characteristics of both phases unambiguously. The pyridine molecules interact in both phases through CH⋯π and CH⋯N interactions. The nature of individual contacts is preserved through the phase transition between phases III and II, which occurs on decompression. A combination of rigid-body symmetry mode analysis and density functional theory calculations enables the soft vibrational lattice mode which governs the transformation to be identified

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

Quasi-molecular and atomic phases of dense solid hydrogen

The high-pressure phases of solid hydrogen are of fundamental interest and relevant to the interior of giant planets; however, knowledge of these phases is far from complete. Particle swarm optimization (PSO) techniques were applied to a structural search, yielding hitherto unexpected high-pressure phases of solid hydrogen at pressures up to 5 TPa. An exotic quasi-molecular mC24 structure (space group C2/c, stable at 0.47-0.59 TPa) with two types of intramolecular bonds was predicted, providing a deeper understanding of molecular dissociation in solid hydrogen, which has been a mystery for decades. We further predicted the existence of two atomic phases: (i) the oC12 structure (space group Cmcm, stable at > 2.1 TPa), consisting of planar H3 clusters, and (ii) the cI16 structure, previously observed in lithium and sodium, stable above 3.5 TPa upon consideration of the zero-point energy. This work clearly revised the known zero-temperature and high-pressure (>0.47 TPa) phase diagram for solid hydrogen and has implications for the constituent structures of giant planets.Comment: accepted in The Journal of Physical Chemistr