Structural and superconducting transition in selenium under high pressures

First-principles calculations are performed for electronic structures of two high pressure phases of solid selenium, $\beta$-Po and bcc. Our calculation reproduces well the pressure-induced phase transition from $\beta$-Po to bcc observed in selenium. The calculated transition pressure is 30 GPa lower than the observed one, but the calculated pressure dependence of the lattice parameters agrees fairly well with the observations in a wide range of pressure. We estimate the superconducting transition temperature $T_{\rm c}$ of both the $\beta$-Po and the bcc phases by calculating the phonon dispersion and the electron-phonon interaction on the basis of density-functional perturbation theory. The calculated $T_{\rm c}$ shows a characteristic pressure dependence, i.e. it is rather pressure independent in the $\beta$-Po phase, shows a discontinuous jump at the transition from $\beta$-Po to bcc, and then decreases rapidly with increasing pressure in the bcc phase.Comment: 8 pages, 11 figure

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

Phonon softening and superconductivity in tellurium under pressure

The phonon dispersion and the electron-phonon interaction for the $\beta$-Po and the bcc high pressure phases of tellurium are computed with density-functional perturbation theory. Our calculations reproduce and explain the experimentally observed pressure dependence of the superconducting critical temperature (T$_{\rm c}$) and confirm the connection between the jump in T$_{\rm c}$ and the structural phase transition. The phonon contribution to the free energy is shown to be responsible for the difference in the structural transition pressure observed in low and room temperature experiments.Comment: Revtex, 4 Postscript figures, to appear in Phys. Rev. Let

Low-Energy Linear Structures in Dense Oxygen: Implications for the ϵ\epsilon-phase

Using density functional theory implemented within the generalized gradient approximation, a new non-magnetic insulating ground state of solid oxygen is proposed and found to be energetically favored at pressures corresponding to the $\epsilon$-phase. The newly-predicted ground state is composed of linear herringbone-type chains of O$_2$ molecules and has {\it Cmcm} symmetry (with an alternative monoclinic cell). Importantly, this phase supports IR-active zone-center phonons, and their computed frequencies are found to be in broad agreement with recent infrared absorption experiments.Comment: 4 pages, 4 figure

Pressure-induced alpha-to-omega transition in titanium metal: A systematic study of the effects of uniaxial stress

We investigated the effects of uniaxial stress on the pressure-induced alpha-to-omega transition in pure titanium (Ti) by means of angle dispersive x-ray diffraction in a diamond-anvil cell. Experiments under four different pressure environments reveal that: (1) the onset of the transition depends on the pressure medium used, going from 4.9 GPa (no pressure medium) to 10.5 GPa (argon pressure medium); (2) the a and w phases coexist over a rather large pressure range, which depends on the pressure medium employed; (3) the hysteresis and quenchability of the w phase is affected by differences in the sample pressure environment; and (4) a short term laser-heating of Ti lowers the alpha-to-omega transition pressure. Possible transition mechanisms are discussed in the light of the present results, which clearly demonstrated the influence of uniaxial stress in the alpha-to-omega transition.Comment: 16 pages, 6 figures, 1 tabl

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

Crystal structure of solid Oxygen at high pressure and low temperature

Results of X-ray diffraction experiments on solid oxygen at low temperature and at pressures up to 10 GPa are presented.A careful sample preparation and annealing around 240 K allowed to obtain very good diffraction patterns in the orthorhombic delta-phase. This phase is stable at low temperature, in contrast to some recent data [Y. Akahama et al., Phys. Rev. B64, 054105 (2001)], and transforms with decreasing pressure into a monoclinic phase, which is identified as the low pressure alpha-phase. The discontinuous change of the lattice parameters, and the observed metastability of the alpha-phase increasing pressure suggest that the transition is of the first order.Comment: 4 pages with three figure