Sub-micrometer focusing setup for high-pressure crystallography at the Extreme Conditions beamline at PETRA†III.

Scientific tasks aimed at decoding and characterizing complex systems and processes at high pressures set new challenges for modern X-ray diffraction instrumentation in terms of X-ray flux, focal spot size and sample positioning. Presented here are new developments at the Extreme Conditions beamline (P02.2, PETRA III, DESY, Germany) that enable considerable improvements in data collection at very high pressures and small scattering volumes. In particular, the focusing of the X-ray beam to the sub-micrometer level is described, and control of the aberrations of the focusing compound refractive lenses is made possible with the implementation of a correcting phase plate. This device provides a significant enhancement of the signal-to-noise ratio by conditioning the beam shape profile at the focal spot. A new sample alignment system with a small sphere of confusion enables single-crystal data collection from grains of micrometer to sub-micrometer dimensions subjected to pressures as high as 200 GPa. The combination of the technical development of the optical path and the sample alignment system contributes to research and gives benefits on various levels, including rapid and accurate diffraction mapping of samples with sub-micrometer resolution at multimegabar pressures.

Revealing the Complex Nature of Bonding in the Binary High-Pressure Compound FeO_{2}.

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe_{2}O_{3} and the appearance of FeO_{2}. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO_{2} and isostructural FeO_{2}H_{0.5} is ferric (Fe^{3+}), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites.

The most incompressible metal osmium at static pressures above 750 gigapascals.

Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression.

Breakdown of Magnetic Order in the Pressurized Kitaev Iridate ß-Li_{2}IrO_{3}.

Temperature-pressure phase diagram of the Kitaev hyperhoneycomb iridate ß-Li_{2}IrO_{3} is explored using magnetization, thermal expansion, magnetostriction, and muon spin rotation measurements, as well as single-crystal x-ray diffraction under pressure and ab initio calculations. The Néel temperature of ß-Li_{2}IrO_{3} increases with the slope of 0.9 K/GPa upon initial compression, but the reduction in the polarization field H_{c} reflects a growing instability of the incommensurate order. At 1.4 GPa, the ordered state breaks down upon a first-order transition, giving way to a new ground state marked by the coexistence of dynamically correlated and frozen spins. This partial freezing in the absence of any conspicuous structural defects may indicate the classical nature of the resulting pressure-induced spin liquid, an observation paralleled to the increase in the nearest-neighbor off-diagonal exchange Γ under pressure.

Role of disorder in the thermodynamics and atomic dynamics of glasses.

We measured the density of vibrational states (DOS) and the specific heat of various glassy and crystalline polymorphs of SiO2. The typical (ambient) glass shows a well-known excess of specific heat relative to the typical crystal (α-quartz). This, however, holds when comparing a lower-density glass to a higher-density crystal. For glassy and crystalline polymorphs with matched densities, the DOS of the glass appears as the smoothed counterpart of the DOS of the corresponding crystal; it reveals the same number of the excess states relative to the Debye model, the same number of all states in the low-energy region, and it provides the same specific heat. This shows that glasses have higher specific heat than crystals not due to disorder, but because the typical glass has lower density than the typical crystal.

An insight into what superconducts in polycrystalline boron-doped diamonds based on investigations of microstructure.

The discovery of superconductivity in polycrystalline boron-doped diamond (BDD) synthesized under high pressure and high temperatures [Ekimov, et al. (2004) Nature 428:542-545] has raised a number of questions on the origin of the superconducting state. It was suggested that the heavy boron doping of diamond eventually leads to superconductivity. To justify such statements more detailed information on the microstructure of the composite materials and on the exact boron content in the diamond grains is needed. For that we used high-resolution transmission electron microscopy and electron energy loss spectroscopy. For the studied superconducting BDD samples synthesized at high pressures and high temperatures the diamond grain sizes are approximately 1-2 mum with a boron content between 0.2 (2) and 0.5 (1) at %. The grains are separated by 10- to 20-nm-thick layers and triangular-shaped pockets of predominantly (at least 95 at %) amorphous boron. These results render superconductivity caused by the heavy boron doping in diamond highly unlikely.

Isothermal equation of state of crystalline and glassy materials from optical measurements in diamond anvil cells.

Here, we present a method to study the equation of state of opaque amorphous and crystalline materials in diamond anvil cells. The approach is based on measurements of sample dimensions using high-resolution optical microscopy. Data on the volumetric strain as a function of pressure allow deriving the isothermal equation of state of the studied material. The analysis of optical images is fully automatized and allows measuring the sample dimensions with the precision of about 60 nm. The methodology was validated by studying isothermal compression of ω-Ti up to 30 GPa in a Ne pressure transmitting medium. Within the accuracy of the measurements, the bulk modulus of ω-Ti determined using optical microscopy was similar to that obtained from x-ray diffraction. For glassy carbon compressed to ∼30 GPa, the previously unknown bulk modulus was found to be equal to K0 = 28 (2) GPa [K' = 5.5(5)].

Portable laser-heating system for diamond anvil cells.

The diamond anvil cell (DAC) technique coupled with laser heating has become the most successful method for studying materials in the multimegabar pressure range at high temperatures. However, so far all DAC laser-heating systems have been stationary: they are linked either to certain equipment or to a beamline. Here, a portable laser-heating system for DACs has been developed which can be moved between various analytical facilities, including transfer from in-house to a synchrotron or between synchrotron beamlines. Application of the system is demonstrated in an example of nuclear inelastic scattering measurements of ferropericlase (Mg(0.88)Fe(0.12))O and h.c.p.-Fe(0.9)Ni(0.1) alloy, and X-ray absorption near-edge spectroscopy of (Mg(0.85)Fe(0.15))SiO(3) majorite at high pressures and temperatures. Our results indicate that sound velocities of h.c.p.-Fe(0.9)Ni(0.1) at pressures up to 50 GPa and high temperatures do not follow a linear relation with density.

Metastable silica high pressure polymorphs as structural proxies of deep Earth silicate melts.

Modelling of processes involving deep Earth liquids requires information on their structures and compression mechanisms. However, knowledge of the local structures of silicates and silica (SiO2) melts at deep mantle conditions and of their densification mechanisms is still limited. Here we report the synthesis and characterization of metastable high-pressure silica phases, coesite-IV and coesite-V, using in situ single-crystal X-ray diffraction and ab initio simulations. Their crystal structures are drastically different from any previously considered models, but explain well features of pair-distribution functions of highly densified silica glass and molten basalt at high pressure. Built of four, five-, and six-coordinated silicon, coesite-IV and coesite-V contain SiO6 octahedra, which, at odds with 3rd Pauling's rule, are connected through common faces. Our results suggest that possible silicate liquids in Earth's lower mantle may have complex structures making them more compressible than previously supposed.

Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content and stability at ambient conditions are mutually exclusive, thereby making the synthesis of such materials challenging. One way to stabilize such compounds is the application of high pressure. Here, through a direct reaction between Fe and N2 in a laser-heated diamond anvil cell, we synthesize three ironnitrogen compounds Fe3N2, FeN2 and FeN4. Their crystal structures are revealed by single-crystal synchrotron X-ray diffraction. Fe3N2, synthesized at 50 GPa, is isostructural to chromium carbide Cr3C2. FeN2 has a marcasite structure type and features covalently bonded dinitrogen units in its crystal structure. FeN4, synthesized at 106 GPa, features polymeric nitrogen chains of [N42-]n units. Based on results of structural studies and theoretical analysis, [N42-]n units in this compound reveal catena-poly[tetraz-1-ene-1,4-diyl] anions.

Portable double-sided pulsed laser heating system for time-resolved geoscience and materials science applications.

A portable double-sided pulsed laser heating system for diamond anvil cells has been developed that is able to stably produce laser pulses as short as a few microseconds with repetition frequencies up to 100 kHz. In situ temperature determination is possible by collecting and fitting the thermal radiation spectrum for a specific wavelength range (particularly, between 650 nm and 850 nm) to the Planck radiation function. Surface temperature information can also be time-resolved by using a gated detector that is synchronized with the laser pulse modulation and space-resolved with the implementation of a multi-point thermal radiation collection technique. The system can be easily coupled with equipment at synchrotron facilities, particularly for nuclear resonance spectroscopy experiments. Examples of applications include investigations of high-pressure high-temperature behavior of iron oxides, both in house and at the European Synchrotron Radiation Facility using the synchrotron Mössbauer source and nuclear inelastic scattering.

Structural complexity of simple Fe2O3 at high pressures and temperatures.

Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

Planetary science. Shock compression of stishovite and melting of silica at planetary interior conditions.

Deep inside planets, extreme density, pressure, and temperature strongly modify the properties of the constituent materials. In particular, how much heat solids can sustain before melting under pressure is key to determining a planet's internal structure and evolution. We report laser-driven shock experiments on fused silica, α-quartz, and stishovite yielding equation-of-state and electronic conductivity data at unprecedented conditions and showing that the melting temperature of SiO2 rises to 8300 K at a pressure of 500 gigapascals, comparable to the core-mantle boundary conditions for a 5-Earth mass super-Earth. We show that mantle silicates and core metal have comparable melting temperatures above 500 to 700 gigapascals, which could favor long-lived magma oceans for large terrestrial planets with implications for planetary magnetic-field generation in silicate magma layers deep inside such planets.

[Modulation of the neuronal activity and evoked potentials of the cerebral cortex by stimulation of the dorsal hippocampus]. / Moduliatsiia neironnoi aktivnosti i vyzvannykh potentsialov kory bol'shikh polusharii razdrazheniem dorzal'nogo gippokampa

In experiments on alert rabbits high frequency stimulation of the CA1 field of the dorsal hippocampus reduced the peak latency of the main negative component of the evoked potential (EP) to a light flash in the sensorimotor and occipital tests areas of the cerebral cortex. A single stimulation of the same part of the hippocampus resulted in a gradually developing facilitation of secondary negativity of the EP 5th component, predominantly in the sensorimotor cortex. Investigation of neuronal responses in the same cortical areas to a stimulation of the CA1 field with different parameters has shown that the effects of EP modulation are due to dynamic reorganizations of cortical neuronal activity.

[Cortical activation: the role of the indeterminacy/determinacy of a situation]. / K probleme korkovoi aktivatsii: rol' neopredelennosti/opredelennosti situatsii.

Ontogenetic data concerning EEG correlates of activation during attention were analysed in various paradigms. The results were compared with the degree of certainty/uncertainty of situation established by the instruction or determined by the subject. A proposition is made about two activation types in human EEG desynchronization and synchronization within the alpha-band. Both activation types which facilitate brain organization of present or forthcoming activity realize it in their own ways. Desynchronization which leads to disintegration of the system promotes formation of the new one. Synchronization immediately facilitates functional integration of brain structures involved into a specific form of activity. The results of processing and evaluation of information which characterize certainty/uncertainty of situation determine the balance between the two activation types.

[Ontogenetic analysis of the EEG-activation reaction in children]. / Ontogeneticheskii analiz EEG-reaktsii aktivatsii u detei.

Frequency characteristics of EEG-reaction have been analysed in children of 3-10 years in the process of realization of the orienting reflex to sound stimuli. An enhancement of theta- and alpha-oscillations has been found in such conditions which becomes less pronounced to 9-10 years. In the last age group, the reaction of blockade of the basic rhythm of the background EEG (alpha-oscillations of 10 Hz) is formed, combined with local enhancement of other rhythmic components of this frequency range. Functional significance of different forms of EEG activation reaction has been determined. The question is discussed of functional heterogeneity of rhythmic components of the alpha-range and their differential involvement in the reaction reflecting complex mechanisms of cortical activation.

[The ontogenetic characteristics of the functional organization of the cerebral hemispheres in selective attention: perceptual task expectancy]. / Ontogeneticheskie osobennosti funktsional'noi organizatsii polusharii mozga pri napravlennom vnimanii: ozhidanie pertseptivnoi zadachi.

EEG characteristics of brain organization of selective attention were studied in children (n = 10, 9 years old) during task expectancy with special reference to hemisphere specialization. Children had to distinguish lateralized signals according to their duration. Warning stimulus pointed to the modality of the task (tactile, auditory, visual). Intra-hemispheric alpha-coherence was evaluated in the prestimulus period with the following statistical analysis of the individual data. The main distinctions of the brain functional organization during expectancy between children and adults consisted in less pronounced selectivity of EEG changes in the left hemisphere and in existence of modal specificity in the right hemisphere in children as compared to adults. Thus, the functional specialization of the hemispheres in children is not yet completely developed. Brain hemispheres of children partly share functions rather than complement each other.

[The functional organization of the cerebral hemispheres during directed attention in children 7 to 8 years old]. / Funktsional'naia organizatsiia polusharii mozga pri napravlennom vnimanii u detei 7--8 let.

Functional organization of brain hemispheres of 15 right-handed 7-8-years-old children was analysed during attention directed to the classification of lateralized auditory and tactile stimuli according to their duration. The subjective task difficulty was equal for all the children. Random presentation of stimuli in series of right and left-side stimulation and visual indication of the forthcoming stimulus modality (warning signal) improved the direction of subject's attention in accordance with the instruction. Monopolar EEGs were recorded from 15 cortical leads in both hemispheres referenced to linked ear lobes. EEG spectral analysis was performed with assessment of spectral power density and coherence of the alpha-range components. The hemisphere dichotomy which had been revealed in adult subjects under the same conditions was shown to be absent in children. Local functional integration of cortical regions around the modality-specific areas (T3, T4 for the auditory and C3, C4 for the tactile stimulation) was found in both hemispheres of children in contrast to the only left hemisphere in adults. The diffuse, modality-independent functional organization of adult right hemisphere was not observed in children. The described features of intrahemispheric organization in both groups provide correct decisions thus characterizing the successful alternative strategies. The grounds of revealed age differences, age-dependent mechanisms of functional hemisphere organization, and nonlinear trend of hemispheric specialization development are discussed.

[Analysis of plastic convergence of sensory signals on neurons of field CA1 of the rabbit dorsal hippocampus]. / Analiz plasticheskoi konvergentsii sensornykh signalov na neironakh polia CA1 dorzal'nogo gippokampa krolika.

Static and dynamic characteristics of unit responses to single and multiple clicks and diffuse light flashes were studied in neurones of CA1 field of the dorsal hippocampus in alert, loosely fixed rabbits. The recorded neurones were characterized by specificity of sensory inputs, selectivity and plastic reorganizations of reactions. Validity of Sokolov model of plastic convergence for neurones of CA1 field and functional significance of the output signal of CA1 field in the system of control of activation processes in OR are discussed.

[Specificity of hippocampal field CA3 neuronal responses to repetitive single stimuli]. / Spetsifika otvetov neironov polia CA3 gippokampa krolika na povtoriaiushchiesia odinochnye stimuly.

It has been shown on alert rabbits that responses of field CA3 units to stimuli eliciting (single tones) and not eliciting (single flashes) an activation reaction are substantially different. 75% of units responsive to a flash exhibited: less pronounced tonic extinctive responses, stable structurized phasic reactions and the dynamics of responses in the form of changes in their types. The system of field CA3 units "triggered" by single stimulation is under control of the sensorimotor cortical area. Modulating cortical influences enhance the revealed tendencies of responses of the examined neurones to a single photic stimulus.