Compressibility and structural stability of ultra-incompressible bimetallic interstitial carbides and nitrides

We have investigated by means of high-pressure x-ray diffraction the structural stability of Pd2Mo3N, Ni2Mo3C0.52N0.48, Co3Mo3C0.62N0.38, and Fe3Mo3C. We have found that they remain stable in their ambient-pressure cubic phase at least up to 48 GPa. All of them have a bulk modulus larger than 330 GPa, being the least compressible material Fe3Mo3C, B0 = 374(3) GPa. In addition, apparently a reduction of compressibility is detected as the carbon content increased. The equation of state for each material is determined. A comparison with other refractory materials indicates that interstitial nitrides and carbides behave as ultra-incompressible materials.Comment: 14 pages, 3 figures, 1 tabl

Structural stability of Fe5Si3 and Ni2Si studied by high-pressure x-ray diffraction and ab initio total-energy calculations

We performed high-pressure angle dispersive x-ray diffraction measurements on Fe5Si3 and Ni2Si up to 75 GPa. Both materials were synthesized in bulk quantities via a solid-state reaction. In the pressure range covered by the experiments, no evidence of the occurrence of phase transitions was observed. On top of that, Fe5Si3 was found to compress isotropically, whereas an anisotropic compression was observed in Ni2Si. The linear incompressibility of Ni2Si along the c-axis is similar in magnitude to the linear incompressibility of diamond. This fact is related to the higher valence-electron charge density of Ni2Si along the c-axis. The observed anisotropic compression of Ni2Si is also related to the layered structure of Ni2Si where hexagonal layers of Ni2+ cations alternate with graphite-like layers formed by (NiSi)2- entities. The experimental results are supported by ab initio total-energy calculations carried out using density functional theory and the pseudopotential method. For Fe5Si3, the calculations also predicted a phase transition at 283 GPa from the hexagonal P63/mcm phase to the cubic structure adopted by Fe and Si in the garnet Fe5Si3O12. The room-temperature equations of state for Fe5Si3 and Ni2Si are also reported and a possible correlation between the bulk modulus of iron silicides and the coordination number of their minority element is discussed. Finally, we report novel descriptions of these structures, in particular of the predicted high-pressure phase of Fe5Si3 (the cation subarray in the garnet Fe5Si3O12), which can be derived from spinel Fe2SiO4 (Fe6Si3O12).Comment: 44 pages, 13 figures, 3 Table

Exploring the high-pressure behavior of the three known polymorphs of BiPO4: Discovery of a new polymorph

The following article appeared in Journal of Applied Physics and may be found at http://dx.doi.org/10.1063/1.4914407 . Authors own version of final article on e-print serversWe have studied the structural behavior of bismuth phosphate under compression. We performed x-ray powder diffraction measurements up to 31.5 GPa and ab initio calculations. Experiments were carried out on different polymorphs: trigonal (phase I) and monoclinic (phases II and III). Phases I and III, at low pressure (P < 0.2-0.8 GPa), transform into phase II, which has a monazite-type structure. At room temperature, this polymorph is stable up to 31.5 GPa. Calculations support these findings and predict the occurrence of an additional transition from the monoclinic monazite-type to a tetragonal scheelite-type structure (phase IV). This transition was experimentally found after the simultaneous application of pressure (28 GPa) and temperature (1500 K), suggesting that at room temperature the transition might by hindered by kinetic barriers. Calculations also predict an additional phase transition at 52 GPa, which exceeds the maximum pressure achieved in the experiments. This transition is from phase IV to an orthorhombic barite-type structure (phase V). We also studied the axial and bulk compressibility of BiPO4. Room-temperature pressure-volume equations of state are reported. BiPO4 was found to be more compressible than isomorphic rare-earth phosphates. The discovered phase IV was determined to be the less compressible polymorph of BiPO4. On the other hand, the theoretically predicted phase V has a bulk modulus comparable with that of monazite-type BiPO4. Finally, the isothermal compressibility tensor for the monazite-type structure is reported at 2.4 GPa showing that the direction of maximum compressibility is in the (0 1 0) plane at approximately 15 degrees (21 degrees) to the a axis for the case of our experimental (theoretical) study. (C) 2015 AIP Publishing LLC.Research supported by the Spanish government MINECO under Grant No: MAT2013-46649-C4-1/2/3-P and by Generalitat Valenciana under Grants Nos. GVA-ACOMP-2013-1012 and GVA-ACOMP/2014/243. B.G.-D. thanks the financial support from MEC through FPI program. Experiments were performed at MSPD beamline at ALBA Synchrotron Light Facility with the collaboration of ALBA staff.Errandonea, D.; Gomis, O.; Santamaría Pérez, D.; García-Domene, B.; Muñoz, A.; Rodríguez-Hernández, P.; Achary, SN.... (2015). Exploring the high-pressure behavior of the three known polymorphs of BiPO4: Discovery of a new polymorph. Journal of Applied Physics. 117:105902-1-105902-9. https://doi.org/10.1063/1.4914407S105902-1105902-911

Phase behaviour of Ag2CrO4 under compression: Structural, vibrational, and optical properties

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp401524sWe have performed an experimental study of the crystal structure, lattice dynamics, and optical properties of silver chromate (Ag2CrO4) at ambient temperature and high pressures. In particular, the crystal structure, Raman-active phonons, and electronic band gap have been accurately determined. When the initial orthorhombic Pnma Ag2CrO4 structure (phase I) is compressed up to 4.5 GPa, a previously undetected phase (phase II) has been observed with a 0.95% volume collapse. The structure of phase II can be indexed to a similar orthorhombic cell as phase I, and the transition can be considered to be an isostructural transition. This collapse is mainly due to the drastic contraction of the a axis (1.3%). A second phase transition to phase III occurs at 13 GPa to a structure not yet determined. First-principles calculations have been unable to reproduce the isostructural phase transition, but they propose the stabilization of a spinel-type structure at 11 GPa. This phase is not detected in experiments probably because of the presence of kinetic barriers. Experiments and calculations therefore seem to indicate that a new structural and electronic description is required to model the properties of silver chromate.This study was supported by the Spanish government MEC under grants MAT2010-21270-C04-01/03/04 and CTQ2009-14596-C02-01, by the Comunidad de Madrid and European Social Fund (S2009/PPQ1551 4161893), by the MALTA Consolider Ingenio 2010 project (CSD2007-00045), and by the Vicerrectorado de Investigacion y Desarrollo of the Universidad Politecnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). A.M. and P.R.-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster. J.A.S. acknowledges Juan de la Cierva Fellowship Program for its financial support. Diamond and ALBA Synchrotron Light Sources are acknowledged for provisions of beam time. We also thank Drs. Peral, Popescu, and Fauth for technical support.Santamaría Pérez, D.; Bandiello, E.; Errandonea, D.; Ruiz-Fuertes, J.; Gomis Hilario, O.; Sans, JÁ.; Manjón Herrera, FJ.... (2013). Phase behaviour of Ag2CrO4 under compression: Structural, vibrational, and optical properties. Journal of Physical Chemistry C. 117(23):12239-12248. https://doi.org/10.1021/jp401524sS12239122481172

Correspondence: Strongly-driven Re + CO2 redox reaction at high-pressure and high-temperature

Santamaría-Perez, D.; Mcguire, C.; Makhluf, A.; Kavner, A.; Chulia-Jordan, R.; Jorda Moret, JL.; Rey Garcia, F.... (2016). Correspondence: Strongly-driven Re + CO2 redox reaction at high-pressure and high-temperature. Nature Communications. 7:1-3. doi:10.1038/ncomms13647S137Yoo, C. S. et al. Crystal structure of carbon dioxide at high pressure: “superhard” polymeric carbon dioxide. Phys. Rev. Lett. 83, 5527–5530 (1999).Santoro, M. et al. Partially collapsed cristobalite structure in the non molecular phase V in CO2 . Proc. Natl Acad. Sci. 109, 5176–5179 (2012).Datchi, F., Mallick, B., Salamat, A. & Ninet, S. Structure of polymeric carbon dioxide CO2-V. Phys. Rev. Lett. 108, 125701 (2012).Santoro, M. et al. Silicon carbonate phase formed from carbon dioxide and silica under pressure. Proc. Natl Acad. Sci. 108, 7689–7692 (2011).Santoro, M. et al. Carbon enters silica forming a cristobalite-type CO2.SiO2 solid solution. Nat. Commun. 5, 3761 (2014).Corma, A., Rey, F., Rius, J., Sabater, M. J. & Valencia, S. Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites. Nature 431, 287–290 (2004).Guth, J.-L., Kessler, H. & Wey, R. in Studies in Surface Science and Catalysis Vol. 28 (eds Murakami, Y., Iijima, A. & Ward, J. W.) 121 (Kodansha-Elsevier, 1986).Santamaria-Perez, D. et al. Exploring the chemical reactivity between carbon dioxide and three transition metals (Au, Pt, and Re) at high-pressure high-temperature conditions. Inorg. Chem. 55, 10793–10799 (2016).Magneli, A. Studies on rhenium oxides. Acta Chem. Scand. 11, 28–33 (1957)

Compressibility systematics of calcite-type borates : An experimental and theoretical structural study on ABO3 (A = Al, Sc, Fe and In)

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C , copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp4124259The structural properties of calcite-type orthoborates ABO(3) (A = Al, Fe, Sc, and In) have been investigated at high pressures up to 32 GPa. They were studied experimentally using synchrotron powder X-ray diffraction and theoretically by means of ab initio total-energy calculations. We found that the calcite-type structure remains stable up to the highest pressure explored in the four studied compounds. Experimental and calculated static geometries (unit-cell parameters and internal coordinates), bulk moduli, and their pressure derivatives are in good agreement. The compressibility along the c axis is roughly three times that along the a axis. Our data clearly indicate that the compressibility of borates is dominated by that of the [AO(6)] octahedral group and depends on the size of the trivalent A cations. An analysis of the relationship between isomorphic borates and carbonates is also presented, which points to the potentiality of considering borates as chemical analogues of the carbonate mineral family.This study was supported by the Spanish government MEC under Grant Nos.: MAT2010-21270-C04-01/03/04 and CTQ2009-14596-C02-01, by MALTA Consolider Ingenio 2010 Project (CSD2007-00045), by Generalitat Valenciana (GVA-ACOMP-2013-1012), and by the Vicerrectorado de Investigacion y Desarrollo of the Universidad Politecnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). We thank ALBA and Diamond synchrotrons for providing beamtime for the XRD experiments. A.M. and P.R-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster. J.A.S. and B.G.-D. acknowledge Juan de la Cierva fellowship and FPI programs for financial support. We are gratefully indebted to Dr. Capponi and Dr. Diehl for supplying us single crystals of AlBO3 and FeBO3, respectively.Santamaría Pérez, D.; Gomis Hilario, O.; Sans, JÁ.; Ortiz, HM.; Vegas, Á.; Errandonea, D.; Ruiz-Fuertes, J.... (2014). Compressibility systematics of calcite-type borates : An experimental and theoretical structural study on ABO3 (A = Al, Sc, Fe and In). Journal of Physical Chemistry C. 118(8):4354-4361. https://doi.org/10.1021/jp4124259S43544361118

Experimental and theoretical confirmation of an orthorhombic phase transition in niobium at high pressure and temperature

Compared to other body-centered cubic (bcc) transition metals, Nb has been the subject of fewer compression studies and there are still aspects of its phase diagram which are unclear. Here, we report a combined theoretical and experimental study of Nb under high pressure and temperature. We present the results of static laser-heated diamond anvil cell experiments up to 120 GPa using synchrotron-based fast x-ray diffraction combined with ab initio quantum molecular dynamics simulations. The melting curve of Nb is determined and evidence for a solid-solid phase transformation in Nb with increasing temperature is found. The high-temperature phase of Nb is orthorhombic Pnma. The bcc-Pnma transition is clearly seen in the experimental data on the Nb principal Hugoniot. The bcc-Pnma coexistence observed in our experiments is explained. Agreement between the measured and calculated melting curves is very good except at 40–60 GPa where three experimental points lie below the theoretical melting curve by 250 K (or 7%); a possible explanation is given

Structural and vibrational study of pseudocubic CdIn2Se4 under compression

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp5077565We report a comprehensive experimental and theoretical study of the structural and vibrational properties of a-CdIn2Se4 under compression. Angle-dispersive synchrotron X-ray diffraction and Raman spectroscopy evidence that this ordered-vacancy compound with pseudocubic structure undergoes a phase transition (7 GPa) toward a disordered rocksalt structure as observed in many other ordered-vacancy compounds. The equation of state and the pressure dependence of the Raman-active modes of this semiconductor have been determined and compared both to ab initio total energy and lattice dynamics calculations and to related compounds. Interestingly, on decreasing pressure, at similar to 2 GPa, CdIn2Se4 transforms into a spinel structure which, according to calculations, is energetically competitive with the initial pseudocubic phase. The phase behavior of this compound under compression and the structural and compressibility trends in AB(2)Se(4) selenides are discussed.This study was supported by the Spanish government MEC under Grant Nos: MAT2013-46649-C4-3-P, MAT2013-46649-C4-2-P, MAT2010-21270-C04-03/04, and CTQ2009-14596-C02-01, by MALTA Consolider Ingenio 2010 Project (CSD2007-00045) and by Generalitat Valenciana (GVA-ACOMP-2013-1012). A.M. and P.R-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster, and also to S. Munoz-Rodriguez for providing a data-parsing application. J.A.S. acknowledges Juan de la Cierva fellowship program for financial support.Santamaría Pérez, D.; Gomis, O.; Pereira, ALJ.; Vilaplana Cerda, RI.; Popescu, C.; Sans Tresserras, JÁ.; Manjón Herrera, FJ.... (2014). Structural and vibrational study of pseudocubic CdIn2Se4 under compression. Journal of Physical Chemistry C. 118(46):26987-26999. https://doi.org/10.1021/jp5077565S26987269991184

Large Magnetoresistance of Isolated Domain Walls in La2/3Sr1/3MnO3 Nanowires

Generation, manipulation, and sensing of magnetic domain walls are cornerstones in the design of efficient spintronic devices. Half-metals are amenable for this purpose as large low field magnetoresistance signals can be expected from spin accumulation at spin textures. Among half metals, La1−xSrxMnO3 (LSMO) manganites are considered as promising candidates for their robust half-metallic ground state, Curie temperature above room temperature (Tc = 360 K, for x = 1/3), and chemical stability. Yet domain wall magnetoresistance is poorly understood, with large discrepancies in the reported values and conflicting interpretation of experimental data due to the entanglement of various source of magnetoresistance, namely, spin accumulation, anisotropic magnetoresistance, and colossal magnetoresistance. In this work, the domain wall magnetoresistance is measured in LSMO cross-shape nanowires with single-domain walls nucleated across the current path. Magnetoresistance values above 10% are found to be originating at the spin accumulation caused by the mistracking effect of the spin texture of the domain wall by the conduction electrons. Fundamentally, this result shows the importance on non-adiabatic processes at spin textures despite the strong Hund coupling to the localized t2g electrons of the manganite. These large magnetoresistance values are high enough for encoding and reading magnetic bits in future oxide spintronic sensors. © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.G.O. and D.S.-M. contributed equally to this work. The authors ac-knowledge received funding from the project To2Dox of FlagERA ERA-NET Cofund in Quantum Technologies implemented within the Euro-pean Union’s Horizon 2020 Program. This work was supported by Span-ish AEI through grants, PID2020-118078RB-I00, PID2020-11556RB-100and PID2020-117024GB-C43 and by Regional Government of MadridCAM through SINERGICO project Y2020/NMT-6661 CAIRO-CM. S.R.-G.also gratefully acknowledges the financial support of the Alexander vonHumboldt foundation. Work at CNRS/Thales supported by French ANR-22CE30-0020 "SUPERFAST". J.J.R was supported by the CSIC program forthe Spanish Recovery, Transformation and Resilience Plan funded by the Recovery and Resilience EU Facility EU regulation 2020/2094. The authorsthank the Helmholtz-Zentrum Berlin für Materialien und Energie for theallocation of synchrotron radiation beamtime.Open access funding enabled and organized by Projekt DEAL.Supporting InformationPeer reviewe

CIBERER : Spanish national network for research on rare diseases: A highly productive collaborative initiative

Altres ajuts: Instituto de Salud Carlos III (ISCIII); Ministerio de Ciencia e Innovación.CIBER (Center for Biomedical Network Research; Centro de Investigación Biomédica En Red) is a public national consortium created in 2006 under the umbrella of the Spanish National Institute of Health Carlos III (ISCIII). This innovative research structure comprises 11 different specific areas dedicated to the main public health priorities in the National Health System. CIBERER, the thematic area of CIBER focused on rare diseases (RDs) currently consists of 75 research groups belonging to universities, research centers, and hospitals of the entire country. CIBERER's mission is to be a center prioritizing and favoring collaboration and cooperation between biomedical and clinical research groups, with special emphasis on the aspects of genetic, molecular, biochemical, and cellular research of RDs. This research is the basis for providing new tools for the diagnosis and therapy of low-prevalence diseases, in line with the International Rare Diseases Research Consortium (IRDiRC) objectives, thus favoring translational research between the scientific environment of the laboratory and the clinical setting of health centers. In this article, we intend to review CIBERER's 15-year journey and summarize the main results obtained in terms of internationalization, scientific production, contributions toward the discovery of new therapies and novel genes associated to diseases, cooperation with patients' associations and many other topics related to RD research