No Arabic abstract
Using density functional theory implemented within the generalized gradient approximation, a new non-magnetic insulating ground state of solid oxygen is proposed and found to be energetically favored at pressures corresponding to the $epsilon$-phase. The newly-predicted ground state is composed of linear herringbone-type chains of O$_2$ molecules and has {it Cmcm} symmetry (with an alternative monoclinic cell). Importantly, this phase supports IR-active zone-center phonons, and their computed frequencies are found to be in broad agreement with recent infrared absorption experiments.
The crystal and magnetic structures of the orthorhombic e-Fe2O3 have been studied by simultaneous Rietveld refinement of X-ray and neutron powder diffraction data in combination with Mossbauer spectroscopy, as well as magnetisation and heat capacity measurements. It has been found that above 150 K the e-Fe2O3 polymorph is a collinear ferrimagnet with the magnetic moments directed along the a axis, while the magnetic ordering below 80 K is characterised by a square-wave incommensurate structure. The transformation between these two states is a second order phase transition and involves subtle structural changes mostly affecting the coordination of the tetrahedral and one of the octahedral Fe sites. The temperature dependence of the e-Fe2O3 magnetic properties is discussed in the light of these results.
H2O is an important constituent in planetary bodies, controlling habitability and, in geologically-active bodies, plate tectonics. At pressures within the interior of many planets, the H-bonds in H2O collapse into stronger, ionic bonds. Here we present agreement between X-ray diffraction and Raman spectroscopy for the transition from ice-VII to ice-X occurring at a pressure of approximately 30.9 GPa by means of combining grain normalizing heat treatment via direct laser heating with static compression. This is evidenced by the emergence of the characteristic Raman mode of cuprite-like ice-X and an abrupt 2.5-fold increase in bulk modulus, implying a significant increase in bond strength. This is preceded by a transition from cubic ice-VII to a structure of tetragonal symmetry, ice-VIIt at 5.1 GPa. Our results significantly shift the mass/radius relationship of water-rich planets and define a high-pressure limit for release of chemically-bound water within the Earth, making the deep mantle a potential long-term reservoir of ancient water.
Systematic studies of the two high-temperature monolayer oxygen structures that exist on the (110) tungsten surface were performed using low-energy electron microscopy and diffraction measurements. Our work questions the commonly accepted interpretation from the literature that striped oxygen superstructures arise from alternating site-exchanged (S-E) domains. We postulate that the superstructures originate from a misfit between tungsten and oxygen lattices while the striped appearance corresponds to a moire pattern. Moreover, we show that the two structures, indicated as 113- and 337-phases due to the characteristic directions of the respective moire patterns, differ considerably in their symmetry properties. This suggests that oxygen atoms in the two overlayers occupy different adsorption sites on average. In particular, the 113-phase features rotational domains that retain mirror symmetries with respect to the [001] and [1-10] directions, whereas the 337-phase is characterized by the appearance of additional domains due to the breaking of these symmetries. We propose structural models for both phases that consistently explain their unusual properties and suggest a universal mechanism for the thermal evolution of oxygen monolayer adsorbed on W(110).
Oxygen is widely used to tune the performance of chalcogenide phase-change materials in the usage of phase-Change random access memory (PCRAM) which is considered as the most promising next-generation non-volatile memory. However, the microscopic role of oxygen in the write-erase process, i.e., the reversible phase transition between crystalline and amorphous state of phase-change materials is not clear yet. Using oxygen doped GeTe as an example, this work unravels the role of oxygen at the atomic scale by means of ab initio total energy calculations and ab initio molecular dynamics simulations. Our main finding is that after the amorphization and the subsequent re-crystallization process simulated by ab initio molecular dynamics, oxygen will drag one Ge atom out of its lattice site and both atoms stay in the interstitial region near the Te vacancy that was originally occupied by the oxygen, forming a dumbbell-like defect (O-VTe-Ge), which is in sharp contrast to the results of ab initio total energy calculations at 0 K showing that the oxygen prefers to substitute Te in crystalline GeTe. This specific defect configuration is found to be responsible for the slower crystallization speed and hence the improved data retention of oxygen doped GeTe as reported in recent experimental work. Moreover, we find that the oxygen will increase the effective mass of the carrier and thus increases the resistivity of GeTe. Our results unravel the microscopic mechanism of the oxygen-doping optimization of phase-change material GeTe, and the present reported mechanism can be applied to other oxygen doped ternary chalcogenide phase-change materials.
Oxygen vacancy formation energy is an important quantity for enabling fast oxygen diffusion and oxygen catalysis in technologies like solid oxide fuel cells. Both previous literature in various systems and our calculations in LaMnO3, La0.75Sr0.25MnO3, LaFeO3, and La0.75Sr0.25FeO3, show mixed results for the direction and magnitude of the change in vacancy formation energy with strain. This paper develops a model to make sense of the different trend shapes in vacancy formation energy versus strain. We model strain effects using a set of consistent ab initio calculations, and demonstrate that our calculated results may be simply explained in terms of vacancy formation volume and changes in elastic constants between the bulk and defected states. A positive vacancy formation volume contributes to decreased vacancy formation energy under tensile strain, and an increase in elastic constants contributes to increases in vacancy formation energy with compressive and tensile strains, and vice versa. The vacancy formation volume dominates the linear portion of the vacancy formation energy strain response, while its curvature is governed by the vacancy-induced change in elastic constants. We show results sensitive to B-site cation, A-site doping, tilt system, and vacancy placement, which contributions may be averaged under thermally averaged conditions. In general, vacancy formation energies for most systems calculated here decreased with tensile strain, with about a 30-100 meV/% strain decrease with biaxial strain for those systems which showed a decrease in vacancy formation energy. Experimental verification is necessary to confirm the model outside of calculation.