Zero-temperature generalized phase diagram of the 4d transition metals under pressure

We use an accurate implementation of density functional theory (DFT) to calculate the zero-temperature generalized phase diagram of the 4$d$ series of transition metals from Y to Pd as a function of pressure $P$ and atomic number $Z$. The implementation used is full-potential linearized augmented plane waves (FP-LAPW), and we employ the exchange-correlation functional recently developed by Wu and Cohen. For each element, we obtain the ground-state energy for several crystal structures over a range of volumes, the energy being converged with respect to all technical parameters to within $\sim 1$ meV/atom. The calculated transition pressures for all the elements and all transitions we have found are compared with experiment wherever possible, and we discuss the origin of the significant discrepancies. Agreement with experiment for the zero-temperature equation of state is generally excellent. The generalized phase diagram of the 4$d$ series shows that the major boundaries slope towards lower $Z$ with increasing $P$ for the early elements, as expected from the pressure induced transfer of electrons from $sp$ states to $d$ states, but are almost independent of $P$ for the later elements. Our results for Mo indicate a transition from bcc to fcc, rather than the bcc-hcp transition expected from $sp$-$d$ transfer.Comment: 28 pages and 10 figures. Submitted to Phys. Rev.

Effect of pressure on the Raman modes of antimony

The effect of pressure on the zone-center optical phonon modes of antimony in the A7 structure has been investigated by Raman spectroscopy. The A_g and E_g frequencies exhibit a pronounced softening with increasing pressure, the effect being related to a gradual suppression of the Peierls-like distortion of the A7 phase relative to a cubic primitive lattice. Also, both Raman modes broaden significantly under pressure. Spectra taken at low temperature indicate that the broadening is at least partly caused by phonon-phonon interactions. We also report results of ab initio frozen-phonon calculations of the A_g and E_g mode frequencies. Presence of strong anharmonicity is clearly apparent in calculated total energy versus atom displacement relations. Pronounced nonlinearities in the force versus displacement relations are observed. Structural instabilities of the Sb-A7 phase are briefly addressed in the Appendix.Comment: 10 pages, 8 figure

Tight-binding study of high-pressure phase transitions in titanium: alpha to omega and beyond

We use a tight-binding total energy method, with parameters determined from a fit to first-principles calculations, to examine the newly discovered gamma phase of titanium. Our parameters were adjusted to accurately describe the alpha Ti-omega Ti phase transition, which is misplaced by density functional calculations. We find a transition from omega Ti to gamma Ti at 102 GPa, in good agreement with the experimental value of 116 GPa. Our results suggest that current density functional calculations will not reproduce the omega Ti-gamma Ti phase transition, but will instead predict a transition from omega Ti to the bcc beta Ti phase.Comment: 3 encapsulated Postscript figures, submitted to Phyical Review Letter

Strained tetragonal states and Bain paths in metals

Paths of tetragonal states between two phases of a material, such as bcc and fcc, are called Bain paths. Two simple Bain paths can be defined in terms of special imposed stresses, one of which applies directly to strained epitaxial films. Each path goes far into the range of nonlinear elasticity and reaches a range of structural parameters in which the structure is inherently unstable. In this paper we identify and analyze the general properties of these paths by density functional theory. Special examples include vanadium, cobalt and copper, and the epitaxial path is used to identify an epitaxial film as related uniquely to a bulk phase.Comment: RevTeX, 4 pages, 4 figures, submitted to Phys. Rev. Let

Boron in copper: a perfect misfit in the bulk and cohesion enhancer at a grain boundary

Our ab initio study suggests that boron segregation to the Sigma 5(310)[001] grain boundary should strengthen the boundary up to 1.5 ML coverage (15.24 at/nm^2). The maximal effect is observed at 0.5 ML and corresponds to boron atoms filling exclusively grain boundary interstices. In copper bulk, B causes significant distortion both in interstitial and regular lattice sites for which boron atoms are either too big or too small. The distortion is compensated to large extent when the interstitial and substitutional boron combine together to form a strongly bound dumbell. Our prediction is that bound boron impurities should appear in sizable proportion if not dominate in most experimental conditions. A large discrepancy between calculated heats of solution and experimental terminal solubility of B in Cu is found, indicating either a sound failure of the local density approximation or, more likely, strongly overestimated solubility limits in the existing B-Cu phase diagram.Comment: 16 pages, 9 figure

The QCD Phase Structure at High Baryon Density

We consider the possibility that color deconfinement and chiral symmetry restoration do not coincide in dense baryonic matter at low temperature. As a consequence, a state of massive "constituent" quarks would exist as an intermediate phase between confined nuclear matter and the plasma of deconfined massless quarks and gluons. We discuss the properties of this state and its relation to the recently proposed quarkyonic matter.Comment: 17 pages, 9 figure

Impact testing to determine the mechanical properties of articular cartilage in isolation and on bone

The original publication is available at www.springerlink.comNon peer reviewedPostprin

Pseudogap formation of four-layer BaRuO3_3 and its electrodynamic response changes

We investiaged the optical properties of four-layer BaRuO$_{3}$, which shows a fermi-liquid-like behavior at low temperature. Its optical conductivity spectra clearly displayed the formation of a pseudogap and the development of a coherent peak with decreasing temperature. Temperature-dependences of the density $n$ and the scattering rate $1/\tau$ of the coherent component were also derived. As the temperature decreases, both $n$ and $1/\tau$ decrease for four-layer BaRuO$_{3}$. These electrodynamic responses were compared with those of nine-layer BaRuO$_{3}$, which also shows a pseudogap formation but has an insulator-like state at low temperature. It was found that the relative rates of change of both $n$ and $1/\tau$ determine either metallic or insulator-like responses in the ruthenates. The optical properties of the four-layer ruthenate were also compared with those of other pseudogap systems, such as high $T_{c}$ cuprates and heavy electron systems.Comment: 7 figures. submitted to Phys. Rev.

Calculations of the A_1 phonon frequency in photoexcited Tellurium

Calculations of the A_1 phonon frequency in photoexcited tellurium are presented. The phonon frequency as a function of photoexcited carrier density and phonon amplitude is determined. Recent pump probe experiments are interpreted in the light of these calculatons. It is proposed that, in conjunction with measurements of the phonon period in ultra-fast pump-probe reflectivity experiments, the calculated frequency shifts can be used to infer the evolution of the density of photoexcited carriers on a sub-picosecond time-scale.Comment: 15 pages Latex, 3 postscript figure

A new interpretation of total column BrO during Arctic spring

Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO “hotspots” during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere