Coexistence of vitreous and crystalline phases of H2O at ambient temperature.

Formation of vitreous ice during rapid compression of water at room temperature is important for biology and the study of biological systems. Here, we show that Raman spectra of rapidly compressed water at greater than 1 GPa at room temperature exhibits the signature of high-density amorphous ice, whereas the X-ray diffraction (XRD) pattern is dominated by crystalline ice VI. To resolve this apparent contradiction, we used molecular dynamics simulations to calculate full vibrational spectra and diffraction patterns of mixtures of vitreous ice and ice VI, including embedded interfaces between the two phases. We show quantitatively that Raman spectra, which probe the local polarizability with respect to atomic displacements, are dominated by the vitreous phase, whereas a small amount of the crystalline component is readily apparent by XRD. The results of our combined experimental and theoretical studies have implications for detecting vitreous phases of water, survival of biological systems under extreme conditions, and biological imaging. The results provide additional insight into the stable and metastable phases of H2O as a function of pressure and temperature, as well as of other materials undergoing pressure-induced amorphization and other metastable transitions.

Evidence from Fermi surface analysis for the low-temperature structure of lithium.

The low-temperature crystal structure of elemental lithium, the prototypical simple metal, is a several-decades-old problem. At 1 atm pressure and 298 K, Li forms a body-centered cubic lattice, which is common to all alkali metals. However, a low-temperature phase transition was experimentally detected to a structure initially identified as having the 9R stacking. This structure, proposed by Overhauser in 1984, has been questioned repeatedly but has not been confirmed. Here we present a theoretical analysis of the Fermi surface of lithium in several relevant structures. We demonstrate that experimental measurements of the Fermi surface based on the de Haas-van Alphen effect can be used as a diagnostic method to investigate the low-temperature phase diagram of lithium. This approach may overcome the limitations of X-ray and neutron diffraction techniques and makes possible, in principle, the determination of the lithium low-temperature structure (and that of other metals) at both ambient and high pressure. The theoretical results are compared with existing low-temperature ambient pressure experimental data, which are shown to be inconsistent with a 9R phase for the low-temperature structure of lithium.

Pressure-Induced Superconductivity and Flattened Se6 Rings in the Wide Band Gap Semiconductor Cu2I2Se6.

The two major classes of unconventional superconductors, cuprates and Fe-based superconductors, have magnetic parent compounds, are layered, and generally feature square-lattice symmetry. We report the discovery of pressure-induced superconductivity in a nonmagnetic and wide band gap 1.95 eV semiconductor, Cu2I2Se6, with a unique anisotropic structure composed of two types of distinct molecules: Se6 rings and Cu2I2 dimers, which are linked in a three-dimensional framework. Cu2I2Se6 exhibits a concurrent pressure-induced metallization and superconductivity at ∼21.0 GPa with critical temperature (Tc) of ∼2.8 K. The Tc monotonically increases within the range of our study reaching ∼9.0 K around 41.0 GPa. These observations coincide with unprecedented chair-to-planar conformational changes of Se6 rings, an abrupt decrease along the c-axis, and negative compression within the ab plane during the phase transition. DFT calculations demonstrate that the flattened Se6 rings within the CuSe layer create a high density of states at the Fermi level. The unique structural features of Cu2I2Se6 imply that superconductivity may emerge in anisotropic Cu-containing materials without square-lattice geometry and magnetic order in the parent compound.

High-pressure superconducting phase diagram of 6Li: isotope effects in dense lithium.

We measured the superconducting transition temperature of (6)Li between 16 and 26 GPa, and report the lightest system to exhibit superconductivity to date. The superconducting phase diagram of (6)Li is compared with that of (7)Li through simultaneous measurement in a diamond anvil cell (DAC). Below 21 GPa, Li exhibits a direct (the superconducting coefficient, α, T(c) proportional M(-α), is positive), but unusually large isotope effect, whereas between 21 and 26 GPa, lithium shows an inverse superconducting isotope effect. The unusual dependence of the superconducting phase diagram of lithium on its atomic mass opens up the question of whether the lattice quantum dynamic effects dominate the low-temperature properties of dense lithium.

Piezochromism and structural and electronic properties of benz[a]anthracene under pressure.

We report a combined experimental and theoretical study of the high pressure behavior of a herringbone-type hydrocarbon benz[a]anthracene (BaA) using fluorescence spectroscopy, X-ray diffraction, optical absorption, photoconductivity measurements, and first-principles density functional theory (DFT) calculations. The ambient-pressure molecular solid phase of BaA was found to be stable up to ∼15.0 GPa. Increasing the external pressure within this region would induce a reversible piezochromic colour change in the sample, from yellow-green to light brown. The reversibility of the colour change was confirmed by both optical observations and fluorescence measurements. Further compression beyond 15 GPa leads to polymerization of the sample and formation of an amorphous hydrogenated carbon. The low pressure crystalline phase is not recoverable when the sample is decompressed from pressure above 15 GPa. DFT investigation of the structures at zero temperature suggests that the formation of a crystalline polymeric phase can take place between 30 and 117 GPa, however the kinetic barriers hinder the process at low pressure regions. The phase transition is therefore suggested to proceed along a gradual transition path to an amorphous phase at a lower reaction threshold, activated by finite temperature effects. Optical absorption measurements reveal that the band gap of BaA decreases at high pressure, from 2.4 eV at 0.5 GPa to 1.0 eV at 50.6 GPa. The DFT calculations further suggest that the band gap of BaA in the molecular phase could reduce to ∼0.1 eV at 117 GPa. Photoconductivity measurements show a continuous increase of photocurrent in the molecular phase region, which most likely originated from the increase of carrier mobility under pressure.

High pressure melting of lithium.

The melting curve of lithium between ambient pressure and 64 GPa is measured by detection of an abrupt change in its electrical resistivity at melting and by visual observation. Here we have used a quasi-four-point resistance measurement in a diamond anvil cell and measured the resistance of lithium as it goes through melting. The resistivity near melting exhibits a well documented sharp increase which allowed us to pinpoint the melting transition from ambient pressure to 64 GPa. Our data show that lithium melts clearly above 300 K in all pressure regions and its melting behavior adheres to the classical model. Moreover, we observed an abrupt increase in the slope of the melting curve around 10 GPa. The onset of this increase fits well to the linear extrapolation of the lower temperature bcc-fcc phase boundary.

Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg3Te2X2 (X = Cl, Br).

Ferroelectricity is typically suppressed under hydrostatic compression because the short-range repulsions, which favor the nonpolar phase, increase more rapidly than the long-range interactions, which prefer the ferroelectric phase. Here, based on single-crystal X-ray diffraction and density-functional theory, we provide evidence of a ferroelectric-like transition from phase I213 to R3 induced by pressure in two isostructural defect antiperovskites Hg3Te2Cl2 (15.5 GPa) and Hg3Te2Br2 (17.5 GPa). First-principles calculations show that this transition is attributed to pressure-induced softening of the infrared phonon mode Γ4, similar to the archetypal ferroelectric material BaTiO3 at ambient pressure. Additionally, we observe a gradual band-gap closing from ~2.5 eV to metallic-like state of Hg3Te2Br2 with an unexpectedly stable R3 phase even after semiconductor-to-metal transition. This study demonstrates the possibility of emergence of polar metal under pressure in this class of materials and establishes the possibility of pressure-induced ferroelectric-like transition in perovskite-related systems.

Quantum and isotope effects in lithium metal.

The crystal structure of elements at zero pressure and temperature is the most fundamental information in condensed matter physics. For decades it has been believed that lithium, the simplest metallic element, has a complicated ground-state crystal structure. Using synchrotron x-ray diffraction in diamond anvil cells and multiscale simulations with density functional theory and molecular dynamics, we show that the previously accepted martensitic ground state is metastable. The actual ground state is face-centered cubic (fcc). We find that isotopes of lithium, under similar thermal paths, exhibit a considerable difference in martensitic transition temperature. Lithium exhibits nuclear quantum mechanical effects, serving as a metallic intermediate between helium, with its quantum effect-dominated structures, and the higher-mass elements. By disentangling the quantum kinetic complexities, we prove that fcc lithium is the ground state, and we synthesize it by decompression.

Deuterium Isotope Effects in Polymerization of Benzene under Pressure.

The enormous versatility in the properties of carbon materials depends on the content of the sp2 and sp3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C6H6 and C6D6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures show the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C6D6 shed light on the mechanism of polymerization of benzene. We find that C6D6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C6D6 is observed.

Effects of Nonhydrostatic Stress on Structural and Optoelectronic Properties of Methylammonium Lead Bromide Perovskite.

We report synchrotron X-ray diffraction, photoconductivity, and photoluminescence investigations of methylammonium-lead-bromide (MAPbBr3) under various stress conditions, supported by density-functional-theory (DFT) calculations. The properties of MAPbBr3 show substantial dependence on the hydrostatic conditions. While nonhydrostatic compression of MAPbBr3 leads to amorphization above 2.4 GPa, under quasi-hydrostatic (Ar) and hydrostatic (He) pressure, the sample remains in crystalline phases. A sequence of phase transitions between two cubic phases and orthorhombic Pnma phase is observed when using Ar, or no pressure-transmitting-medium (PTM). In helium-PTM only transitions between the two cubic structures and a new isostructural phase transition with a large volume collapse to a third cubic-phase at 2.7 GPa was observed. The photoluminescence measurements indicate a pressure-induced band gap-narrowing in the cubic phase I, and a blue-shift in the orthorhombic structure. DFT calculations illustrate that the dynamics of the organic molecules and the inorganic lattice, coupled via the N-H···Br hydrogen-bonding interactions, affect the Pb-Br distance and the bandgap evolution under pressure.

Note: Simple and portable setup for loading high purity liquids in diamond anvil cell.

Here we explain a simple and inexpensive procedure to preserve the original purity of the liquid samples during the loading process in a diamond anvil cell. The idea is to keep the sample in frozen form during the loading process while preventing the condensation of the water or other introduction of contaminants. The system can be quickly and easily assembled in a basic laboratory setup. This process can be used for loading some of the common pressure media in a diamond anvil cell.

Boundaries for martensitic transition of (7)Li under pressure.

Physical properties of lithium under extreme pressures continuously reveal unexpected features. These include a sequence of structural transitions to lower symmetry phases, metal-insulator-metal transition, superconductivity with one of the highest elemental transition temperatures, and a maximum followed by a minimum in its melting line. The instability of the bcc structure of lithium is well established by the presence of a temperature-driven martensitic phase transition. The boundaries of this phase, however, have not been previously explored above 3 GPa. All higher pressure phase boundaries are either extrapolations or inferred based on indirect evidence. Here we explore the pressure dependence of the martensitic transition of lithium up to 7 GPa using a combination of neutron and X-ray scattering. We find a rather unexpected deviation from the extrapolated boundaries of the hR3 phase of lithium. Furthermore, there is evidence that, above ∼3 GPa, once in fcc phase, lithium does not undergo a martensitic transition.

Twin sample chamber for simultaneous comparative transport measurements in a diamond anvil cell.

In static high pressure experiments, performed within a diamond anvil cell (DAC), several different methods of thermometry may be employed to determine the temperature of the sample. Due to different DAC designs or particular experimental designs or goals, uncertainties in the determination of the temperature of a given sample exist. To overcome the inaccuracy in comparing the temperature dependence of transport properties of different materials at high pressure, we have used a novel design of resistivity measurement in a twin sample chamber built on an insulated gasket in a DAC. In this design, the transport properties of two samples will be measured simultaneously and therefore the two samples will always be in the same relative temperatures. The uncertainties in the temperatures of the two samples will be exactly the same and therefore their relative phase diagram will be compared precisely. The pressures of the chambers can be slightly different and is easily determined by the ruby pieces placed in each chamber. To demonstrate the feasibility of this method we have compared the superconducting properties of two YBa2Cu3O(7-x) (0 ≤ x ≤ 0.65) samples with slightly different superconducting transition temperatures at ambient pressure as a function of pressures up to 11 GPa. The upper limit of the pressure achieved using this design would be lower than single chamber gaskets. The highest achievable pressure, as in a conventional single hole setup, depends upon the thickness of the gasket, the culet size, the size, and symmetry of the sample chamber. For the twin chamber, it also depends upon the separation of the holes from each other as well as from the edge of the culet.

Superconductivity of BaLi4 under pressure.

We studied the pressure-induced superconductivity of BaLi4 up to 53 GPa by means of electrical resistivity in a diamond anvil cell. Superconductivity in BaLi4 is first observed at a pressure of 5.4 GPa with a superconducting critical temperature (Tc) of 4.5 K. Below 2 GPa, superconductivity is not observed above the minimum temperature achievable in the current study, 2 K. Between 5.4 and 12 GPa, the Tc increases steeply to its maximum value of 7 K. Above 12 GPa, the pressure dependence of Tc is complex and the sign of dTc/dP changes several times in going up to the maximum pressure studied, of 53 GPa.

Melting line of hydrogen at high pressures.

The insulator to metal transition in solid hydrogen was predicted over 70 years ago but the demonstration of this transition remains a scientific challenge. In this regard, a peak in the temperature versus pressure melting line of hydrogen may be a possible precursor for metallization. However, previous measurements of the fusion curve of hydrogen have been limited in pressure and temperature by diffusion of hydrogen into the gasket or diamonds. To overcome this limitation we have used an innovative technique of pulsed laser heating of the sample and find a peak in the melting line at P=64.7+/-4 GPa and T=1055+/-20 K.

Temperature dependence of the emissivity of platinum in the IR.

The accuracy of temperature determination by fitting the spectral irradiance to a Planck curve depends on knowledge of the emissivity at all temperatures and pressures of interest within a spectral region. Here, the emissivity of platinum is measured in the near infrared as a function of temperature. In the wavelength range of study and the temperature range of 650-1100 K, we find the emissivity to be independent of temperature to within experimental error. This result should lead to improved accuracy of temperature measurement by optical pyrometry where platinum is used as a thermal emitter.

Superconducting phase diagram of Li metal in nearly hydrostatic pressures up to 67 GPa.

The dependence of the superconducting transition temperature T(c) on nearly hydrostatic pressure has been determined to 67 GPa in an ac susceptibility measurement for a Li sample embedded in helium pressure medium. With increasing pressure, superconductivity appears at 5.47 K for 20.3 GPa, T(c) rising rapidly to approximately 14 K at 30 GPa. The T(c)(P) dependence to 67 GPa differs significantly from that observed in previous studies where no pressure medium was used. Evidence is given that superconductivity in Li competes with symmetry breaking structural phase transitions which occur near 20, 30, and 62 GPa. In the pressure range 20-30 GPa, T(c) is found to decrease rapidly in a dc magnetic field, the first evidence that Li is a type I superconductor.