Spiral Chain O4 Form of Dense Oxygen

Oxygen is in many ways a unique element: the only known diatomic molecular magnet and the capability of stabilization of the hitherto unexpected O8 cluster structure in its solid form at high pressure. Molecular dissociations upon compression as one of the fundamental problems were reported for other diatomic solids (e.g., H2, I2, Br2, and N2), but it remains elusive for solid oxygen, making oxygen an intractable system. We here report the theoretical prediction on the dissociation of molecular oxygen into a polymeric spiral chain O4 structure (\theta-O4) by using first-principles calypso method on crystal structure prediction. The \theta-O4 stabilizes above 2 TPa and has been observed as the third high pressure phase of sulfur (S-III). We find that the molecular O8 phase remains extremely stable in a large pressure range of 0.008 - 2 TPa, whose breakdown is driven by the pressure-induced instability of a transverse acoustic phonon mode at zone boundary, leading to the ultimate formation of \theta-O4. Remarkably, stabilization of \theta-O4 turns oxygen from a superconductor into an insulator with a wide band gap (approximately 5.9 eV) originating from the sp3-like hybridized orbitals of oxygen and the localization of valence electrons. (This is a pre-print version of the following article: Li Zhu et al, Spiral chain O4 form of dense oxygen, Proc. Natl. Acad. Sci. U.S.A. (2011), doi: 10.1073/pnas.1119375109, which has been published online at http://www.pnas.org/content/early/2011/12/27/1119375109 .)Comment: 13 apages, 3 figure

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

Simple Metals at High Pressure

In this lecture we review high-pressure phase transition sequences exhibited by simple elements, looking at the examples of the main group I, II, IV, V, and VI elements. General trends are established by analyzing the changes in coordination number on compression. Experimentally found phase transitions and crystal structures are discussed with a brief description of the present theoretical picture.Comment: 22 pages, 4 figures, lecture notes for the lecture given at the Erice course on High-Pressure Crystallography in June 2009, Sicily, Ital

Large amplitude fluxional behaviour of elemental calcium under high pressure

Experimental evidences are presented showing unusually large and highly anisotropic vibrations in the “simple cubic” (SC) unit cell adopted by calcium over a broad pressure ranging from 30–90 GPa and at temperature as low as 40 K. X-ray diffraction patterns show a preferential broadening of the (110) Bragg reflection indicating that the atomic displacements are not isotropic but restricted to the [110] plane. The unusual observation can be rationalized invoking a simple chemical perspective. As the result of pressure-induced s → d transition, Ca atoms situated in the octahedral environment of the simple cubic structure are subjected to Jahn-Teller distortions. First-principles molecular dynamics calculations confirm this suggestion and show that the distortion is of dynamical nature as the cubic unit cell undergoes large amplitude tetragonal fluctuations. The present results show that, even under extreme compression, the atomic configuration is highly fluxional as it constantly changes

Band Gap Closure, Incommensurability and Molecular Dissociation of Dense Chlorine

Molecular systems are predicted to transform into atomic solids and be metallic at high pressure; this was observed for the diatomic elements iodine and bromine. Here the authors access the higher pressures needed to observe the dissociation in chlorine, through an incommensurate phase, and provide evidence for metallization

Conducting linear chains of sulphur inside carbon nanotubes

Despite extensive research for more than 200 years, the experimental isolation of monatomic sulphur chains, which are believed to exhibit a conducting character, has eluded scientists. Here we report the synthesis of a previously unobserved composite material of elemental sulphur, consisting of monatomic chains stabilized in the constraining volume of a carbon nanotube. This one-dimensional phase is confirmed by high-resolution transmission electron microscopy and synchrotron X-ray diffraction. Interestingly, these one-dimensional sulphur chains exhibit long domain sizes of up to 160 nm and high thermal stability (∼800 K). Synchrotron X-ray diffraction shows a sharp structural transition of the one-dimensional sulphur occurring at ∼450-650 K. Our observations, and corresponding electronic structure and quantum transport calculations, indicate the conducting character of the one-dimensional sulphur chains under ambient pressure. This is in stark contrast to bulk sulphur that needs ultrahigh pressures exceeding ∼90 GPa to become metallic