A. M. dos Santos

Large-volume diamond cells for neutron diffraction above 90 GPa

Quantitative high pressure neutron-diffraction measurements have traditionally required large sample volumes of at least ∼25 mm3 due to limited neutron flux. Therefore, pressures in these experiments have been limited to below 25 GPa. In comparison, for X-ray diffraction, sample volumes in conventional diamond cells for pressures up to 100 GPa have been less than 1×10−4 mm3. Here, we report a new design of strongly supported conical diamond anvils for neutron diffraction that has reached 94 GPa with a sample volume of ∼2×10−2 mm3, a 100-fold increase. This sample volume is sufficient to measure full neutron-diffraction patterns of D2O–ice to this pressure at the high flux Spallation Neutrons and Pressure beamline at the Oak Ridge National Laboratory. This provides an almost fourfold extension of the previous pressure regime for such measurements.

Entanglement and Bell's inequality violation above room temperature in metal carboxylates.

In the present work we show that a particular family of materials, the metal carboxylates, may have entangled states up to very high temperatures. From magnetic-susceptibility measurements, we have estimated the critical temperature below which entanglement exists in the copper carboxylate {Cu-2(O2CH)(4)}{Cu(O2CH)(2)(2-methylpyridine)(2)}, and we have found this to be above room temperature (T-e similar to 630 K). Furthermore, the results show that the system remains maximally entangled until close to similar to 100 K and the Bells inequality is violated up to nearly room temperature (similar to 290 K).

Cage occupancies in the high pressure structure H methane hydrate: A neutron diffraction study

A neutron diffraction study was performed on the CD(4) : D(2)O structure H clathrate hydrate to refine its CD(4) fractional cage occupancies. Samples of ice VII and hexagonal (sH) methane hydrate were produced in a Paris-Edinburgh press and in situ neutron diffraction data collected. The data were analyzed with the Rietveld method and yielded average cage occupancies of 3.1 CD(4) molecules in the large 20-hedron (5(12)6(8)) cages of the hydrate unit cell. Each of the pentagonal dodecahedron (5(12)) and 12-hedron (4(3)5(6)6(3)) cages in the sH unit cell are occupied with on average 0.89 and 0.90 CD(4) molecules, respectively. This experiment avoided the co-formation of Ice VI and sH hydrate, this mixture is more difficult to analyze due to the proclivity of ice VI to form highly textured crystals, and overlapping Bragg peaks of the two phases. These results provide essential information for the refinement of intermolecular potential parameters for the water-methane hydrophobic interaction in clathrate hydrates and related dense structures.

Understanding the role played by Fe on the tuning of magnetocaloric effect in Tb5Si2Ge2

In this letter, it is shown that when replacing Ge by Fe in Tb5Si2Ge2 the structural transition still occurs and enhances the magnetocaloric effect (MCE) (up to 66%) with maximum of MCE at a critical Fe amount where the magnetic and structural transitions become fully coupled. It is observed that Fe concentration is able to mimic the effect of external pressure as it induces a complex microstructure, that tunes long range strain fields. This knowledge is crucial for the development of strategies toward materials with improved performance for efficient magnetic refrigeration applications.

Entanglement temperature in molecular magnets composed of S-spin dimers

In the present work, we investigate the quantum thermal entanglement in molecular magnets composed of dimers of spin S, using an Entanglement Witness built from measurements of magnetic susceptibility. An entanglement temperature, Te, is then obtained for some values of spin S. From this, it is shown that Te is proportional to the intradimer exchange interaction J and that entanglement appears only for antiferromagnetic coupling. The results are compared to experiments carried on three isostructural materials: KNaMSi4O10 (M=Mn, Fe or Cu).

Emergence of long-range order in sheets of magnetic dimers

Significance Magnetic materials are composed of individual spins that interact with each other and under suitable conditions can arrange themselves in an ordered array. When spins are confined to two-dimensional sheets, small perturbations can disrupt their order and destroy the magnetic state. We show how a set of interacting, quantum-mechanical spins placed on the corners of a square array evolves from a set of locally bonded entities to a globally ordered structure. The system stabilizes itself against fluctuations through subtle local contractions, elongations, and tilts. The combination of neutron and X-ray scattering at pressures up to 60,000 atmospheres reveals the complex interplay of structural distortions and spin alignments that permit long-range order to emerge in this model quantum magnet. Quantum spins placed on the corners of a square lattice can dimerize and form singlets, which then can be transformed into a magnetic state as the interactions between dimers increase beyond threshold. This is a strictly 2D transition in theory, but real-world materials often need the third dimension to stabilize long-range order. We use high pressures to convert sheets of Cu2+ spin 1/2 dimers from local singlets to global antiferromagnet in the model system SrCu2(BO3)2. Single-crystal neutron diffraction measurements at pressures above 5 GPa provide a direct signature of the antiferromagnetic ordered state, whereas high-resolution neutron powder and X-ray diffraction at commensurate pressures reveal a tilting of the Cu spins out of the plane with a critical exponent characteristic of 3D transitions. The addition of anisotropic, interplane, spin–orbit terms in the venerable Shastry–Sutherland Hamiltonian accounts for the influence of the third dimension.

Evidence for entanglement at high temperatures in an engineered molecular magnet

The molecular compound [Fe2(μ2-oxo)(C3H4N2)6(C2O4)2] was designed and synthesized for the first time and its structure was determined using single-crystal X-ray diffraction. The magnetic susceptibility of this compound was measured from 2 to 300 K. The analysis of the susceptibility data using protocols developed for other spin singlet ground-state systems indicates that the quantum entanglement would remain at temperatures up to 732 K, significantly above the highest entanglement temperature reported to date. The large gap between the ground state and the first-excited state (282 K) suggests that the spin system may be somewhat immune to decohering mechanisms. Our measurements strongly suggest that molecular magnets are promising candidate platforms for quantum information processing.

Heptacopper(II) and dicopper(II)-adenine complexes: synthesis, structural characterization, and magnetic properties

The syntheses, crystal structures, and magnetic properties of two new copper(II) complexes with molecular formulas [Cu7(μ2-OH2)6(μ3-O)6(adenine)6](NO3)2·6H2O (1) and [Cu2(μ2-H2O)2(adenine)2(H2O)4](NO3)4·2H2O (2) are reported. The heptanuclear compound is composed of a central octahedral CuO6 core sharing edges with six adjacent copper octahedra. In 2, the copper octahedra shares one equatorial edge. In both compounds, these basic copper cluster units are further linked by water bridges and bridging adenine ligands through N3 and N9 donors. All copper(II) centers exhibit Jahn–Teller distorted octahedral coordination characteristic of a d9 center. The study of the magnetic properties of the heptacopper complex revealed a dominant ferromagnetic intra-cluster interaction, while the dicopper complex exhibits antiferromagnetic intra-dimer interactions with weakly ferromagnetic inter-dimer interaction. Graphical abstract

Temperature and pressure dependence of the Fe-specific phonon density of statesin Ba(Fe_(1−x)Co_x)_2As_2

The ^(57)Fe-specific phonon density of states (DOS) of Ba(Fe_(1−x)Co_x)_2As_2 single crystals (x=0.0,0.08) was measured at cryogenic temperatures and at high pressures with nuclear-resonant inelastic x-ray scattering. Measurements were conducted for two different orientations of the single crystals, yielding the orientation-projected ^(57)Fe-phonon density of states for phonon polarizations in-plane and out-of-plane with respect to the basal plane of the crystal structure. In the tetragonal phase at 300 K, a clear stiffening was observed upon doping with Co. Increasing pressure to 4 GPa caused a marked increase of phonon frequencies, with the doped material still stiffer than the parent compound. Upon cooling, both the doped and undoped samples showed a stiffening and the parent compound exhibited a discontinuity across the magnetic and structural phase transitions. These findings are generally compatible with the changes in volume of the system upon doping, increasing pressure, or increasing temperature, but an extra softening of high-energy modes occurs with increasing temperature. First-principles computations of the phonon DOS were performed and showed an overall agreement with the experimental results, but underestimate the Gruneisen parameter. This discrepancy is explained in terms of a magnetic Gruneisen parameter, causing an extra phonon stiffening as magnetism is suppressed under pressure.

Radiation attenuation by single-crystal diamond windows

As artificial diamond becomes more cost effective it is likely to see increasing use as a window for sample environment equipment used in diffraction experiments. Such windows are particularly useful as they exhibit exceptional mechanical properties in addition to being highly transparent to both X-ray and neutron radiation. A key application is in high-pressure studies, where diamond anvil cells (DACs) are used to access extreme sample conditions. However, despite their utility, an important consideration when using single-crystal diamond windows is their interaction with the incident beam. In particular, the Bragg condition will be satisfied for specific angles and wavelengths, leading to the appearance of diamond Bragg spots on the diffraction detectors but also, unavoidably, to loss of transmitted intensity of the beam that interacts with the sample. This effect can be particularly significant for energy-dispersive measurements, for example, in time-of-flight neutron diffraction work using DACs. This article presents a semi-empirical approach that can be used to correct for this effect, which is a prerequisite for the accurate determination of diffraction intensities.