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"dos Santos, António M."
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Taxonomic revision and molecular phylogeny of Pisa (Decapoda: Majoidea: Epialtidae), including the description of a new genus of Pisinae
by
Lopes, Evandro P.
,
García-Raso, J. Enrique
,
Gónzalez, José A.
in
Afropisa n. gen
,
Animal morphology
,
Aquatic crustaceans
2023
The spider crabs of the genus Pisa Leach, 1814 (Epialtidae: Pisinae) are reviewed in this study based on morphological and molecular data (16S and COI genes). From these results, a new genus, Afropisa n. gen., is established for the clade composed of Pisa carinimana Miers, 1879, Pisa calva Forest and Guinot, 1966 and Pisa sanctaehelenae Chace, 1966 based on carapace morphology, rostrum, pterygostomian tubercles and male gonopod 1. Additionally, Lissa chiragra (Fabricius, 1775) is transferred to Pisa based on morphological (adults and larvae) and molecular evidence. Furthermore, the status of Pisa hirticornis (Herbst, 1804) is discussed and clarified. The phylogenetic relationships between several Pisinae Dana, 1851 genera, as revealed by molecular data, are discussed. An illustrated identification key of eastern Atlantic and Mediterranean species of Pisinae is provided.
Journal Article
Neutron diffraction observations of interstitial protons in dense ice
2013
The motif of distinct H ₂O molecules in H-bonded networks is believed to persist up to the densest molecular phase of ice. At even higher pressures, where the molecule dissociates, it is generally assumed that the proton remains localized within these same networks. We report neutron-diffraction measurements on D ₂O that reveal the location of the D atoms directly up to 52 GPa, a pressure regime not previously accessible to this technique. The data show the onset of a structural change at ∼13 GPa and cannot be described by the conventional network structure of ice VII above ∼26 GPa. Our measurements are consistent with substantial deuteron density in the octahedral, interstitial voids of the oxygen lattice. The observation of this “interstitial” ice VII form provides a framework for understanding the evolution of hydrogen bonding in ice that contrasts with the conventional picture. It may also be a precursor for the superionic phase reported at even higher pressure with important consequences for our understanding of dense matter and planetary interiors.
Journal Article
Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO3
2015
SignificanceThe steric activity of the lone pair electrons of Pb2+-containing compounds distorts the crystal structure and produces exotic physical properties. In ferroelectric PbTiO3 and PbVO3, the lone-pair electrons hybridizing with the oxygen lead to polarized MO6 octahedra. In PbRuO3, the hybridization induces unprecedented Pb-Ru bonds at high pressure. The sterochemical effect in PbCrO3 makes Pb bond with oxygen without a long-range periodicity. Under the influence of displaced Pb2+, Cr4+ undergoes a charge disproportionation that opens up a gap. In contrast to the pressure effect on PbTiO3 and PbRuO3, pressure restores the undistorted perovskite structure in PbCrO3. This result implies that the sterochemical effect of Pb2+ in a perovskite depends sensitively on the number and energy of the d electrons.
The perovskite PbCrO3 is an antiferromagnetic insulator. However, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. We report a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. We argue that a charge disproportionation 3Cr4+ → 2Cr3+ + Cr6+ in association with the 6s-p hybridization on the Pb2+ is responsible for the insulating ground state of PbCrO3 at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT+U) calculations.
Journal Article
Direct observation of symmetrization of hydrogen bond in δ-AlOOH under mantle conditions using neutron diffraction
by
Kagi, Hiroyuki
,
Hattori, Takanori
,
Tulk, Christopher A.
in
704/2151/2809
,
704/2151/330
,
Diffraction
2018
At ambient pressure, the hydrogen bond in materials such as ice, hydrates, and hydrous minerals that compose the Earth and icy planets generally takes an asymmetric O-H···O configuration. Pressure significantly affects this configuration, and it is predicted to become symmetric, such that the hydrogen is centered between the two oxygen atoms at high pressure. Changes of physical properties of minerals relevant to this symmetrization have been found; however, the atomic configuration around this symmetrization has remained elusive so far. Here we observed the pressure response of the hydrogen bonds in the aluminous hydrous minerals δ-AlOOH and δ-AlOOD by means of a neutron diffraction experiment. We find that the transition from
P
2
1
nm
to
Pnnm
at 9.0 GPa, accompanied by a change in the axial ratios of δ-AlOOH, corresponds to the disorder of hydrogen bond between two equivalent sites across the center of the O···O line. Symmetrization of the hydrogen bond is observed at 18.1 GPa, which is considerably higher than the disorder pressure. Moreover, there is a significant isotope effect on hydrogen bond geometry and transition pressure. This study indicates that disorder of the hydrogen bond as a precursor of symmetrization may also play an important role in determining the physical properties of minerals such as bulk modulus and seismic wave velocities in the Earth’s mantle.
Journal Article
Characterization of Crystallographic Structures Using Bragg-Edge Neutron Imaging at the Spallation Neutron Source
2017
Over the past decade, wavelength-dependent neutron radiography, also known as Bragg-edge imaging, has been employed as a non-destructive bulk characterization method due to its sensitivity to coherent elastic neutron scattering that is associated with crystalline structures. Several analysis approaches have been developed to quantitatively determine crystalline orientation, lattice strain, and phase distribution. In this study, we report a systematic investigation of the crystal structures of metallic materials (such as selected textureless powder samples and additively manufactured (AM) Inconel 718 samples), using Bragg-edge imaging at the Oak Ridge National Laboratory (ORNL) Spallation Neutron Source (SNS). Firstly, we have implemented a phenomenological Gaussian-based fitting in a Python-based computer called iBeatles. Secondly, we have developed a model-based approach to analyze Bragg-edge transmission spectra, which allows quantitative determination of the crystallographic attributes. Moreover, neutron diffraction measurements were carried out to validate the Bragg-edge analytical methods. These results demonstrate that the microstructural complexity (in this case, texture) plays a key role in determining the crystallographic parameters (lattice constant or interplanar spacing), which implies that the Bragg-edge image analysis methods must be carefully selected based on the material structures.
Journal Article
Topological metal-insulator transition within the ferromagnetic state
by
Papadopoulos, Konstantinos
,
Månsson, Martin
,
Takagi, Hidenori
in
639/766/119/2792
,
639/766/119/2795
,
639/766/119/997
2026
A major challenge in condensed matter physics is integrating topological phenomena with correlated electron physics to leverage both types of states for next-generation quantum devices. Metal-insulator transitions are central to bridging these two domains while simultaneously serving as on-off switches for electronic states. Here, we demonstrate how the prototypical material of K
2
Cr
8
O
16
undergoes a ferromagnetic metal-insulator transition accompanied by a change in band topology. Through inelastic x-ray and neutron scattering experiments combined with first-principles theoretical calculations, we show that this transition is not driven by a Peierls mechanism, given the lack of phonon softening. Instead, we establish the transition as a topological metal-insulator transition within the ferromagnetic phase with potential axionic properties, where electron correlations play a key role in stabilizing the insulating state. These results reveal how a metal-insulator transition provides a pathway through which magnetism, topology, and electronic correlations interact.
Combining topological phenomena with correlated electron physics could help enable next-generation quantum devices. Here, the authors demonstrate a topological metal-insulator transition within the ferromagnetic phase of K
2
Cr
8
O
16
.
Journal Article
Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO
2015
The perovskite PbCrO ₃ is an antiferromagnetic insulator. However, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. We report a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. We argue that a charge disproportionation 3Cr ⁴⁺ → 2Cr ³⁺ + Cr ⁶⁺ in association with the 6s-p hybridization on the Pb ²⁺ is responsible for the insulating ground state of PbCrO ₃ at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT+U) calculations.
Significance The steric activity of the lone pair electrons of Pb ²⁺-containing compounds distorts the crystal structure and produces exotic physical properties. In ferroelectric PbTiO ₃ and PbVO ₃, the lone-pair electrons hybridizing with the oxygen lead to polarized MO ₆ octahedra. In PbRuO ₃, the hybridization induces unprecedented Pb-Ru bonds at high pressure. The sterochemical effect in PbCrO ₃ makes Pb bond with oxygen without a long-range periodicity. Under the influence of displaced Pb ²⁺, Cr ⁴⁺ undergoes a charge disproportionation that opens up a gap. In contrast to the pressure effect on PbTiO ₃ and PbRuO ₃, pressure restores the undistorted perovskite structure in PbCrO ₃. This result implies that the sterochemical effect of Pb ²⁺ in a perovskite depends sensitively on the number and energy of the d electrons.
Journal Article
Boundaries for martensitic transition of 7Li under pressure
by
Sinogeikin, Stanislav
,
Deemyad, Shanti
,
Olejnik, Ella
in
639/301/119/1003
,
639/301/119/2795
,
Boundaries
2015
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.
Lithium metal under extreme pressures shows a sequence of structural phase transitions. Here, the authors use neutron scattering and X-ray diffraction techniques under high pressure to expand the experimental phase diagram of lithium, showing an unexpected deviation from existing boundaries.
Journal Article
High-pressure neutron diffraction study on H–D isotope effects in brucite
by
Chakoumakos, Bryan C
,
Horita, Juske
,
dos Santos, António M
in
08 HYDROGEN
,
AMBIENT TEMPERATURE
,
Brucite
2010
A neutron powder diffraction study of hydrogenated and deuterated brucite was conducted at ambient temperature and at pressures up to 9 GPa, using a Paris–Edinburgh high-pressure cell at the WAND instrument of the ORNL High Flux Isotope Reactor. The two materials were synthesized by the same method and companion measurements of neutron diffraction were conducted under the same conditions. Our refinement results show that the lattice-parameters of the a axis, parallel to the sheets of Mg–O octahedra, decrease only slightly with pressure with no effect of H–D substitution. However, the c axis of Mg(OD)2 is shorter and may exhibit greater compressibility with pressure than that of Mg(OH)2. Consequently, the unit-cell volume of deuterated brucite is slightly, but systematically smaller than that of hydrogenated brucite. When fitted to a third-order Birch–Murnaghan equation in terms of the normalized unit-cell volume, values of the bulk modulus for hydrogenated and deuterated brucite (K0 = 39.0 ± 2.8 and 40.4 ± 1.3 GPa, respectively) are, however, indistinguishable from each other within the experimental errors. The measured effect of H–D substitution on the unit-cell volume also demonstrates that brucite (and other hydrous minerals) preferentially incorporate deuterium over hydrogen under pressure, suggesting that the distribution of hydrogen isotopes in deep-earth conditions may differ significantly from that in near-surface environments.
Journal Article