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Results for “Structural phase transition”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,639 records · Page 91
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Thick strings, the liquid crystal blue phase, and cosmological large-scale structure

A phenomenological model based on the liquid crystal blue phase is proposed as a model for a late-time cosmological phase transition. Topological defects, in particular thick strings and/or domain walls, are presented as seeds for structure formation. It is shown that the observed large-scale structure, including quasi-periodic wall structure, can be well fitted in the model without violating the microwave background isotropy bound or the limits from induced gravitational waves and the millisecond pulsar timing. Furthermore, such late-time transitions can produce objects such as quasars at high redshifts. The model appears to work with either cold or hot dark matter.

Luo, Xiaochun↗
DOE OSTI2021

Oval-cycloidal Magnetic Structure with Phase-shift in the Non-centrosymmetric Tetragonal Compound CePdSi 3

CePdSi 3 with H // [100] exhibits multiple metamagnetic transitions. Since there is no frustration in this system, it is suggested that the origin of the multiple metamagnetic transitions is the influence of the antisymmetric spin–orbit interaction. To clarify the magnetic structure under the influence of the antisymmetric spin–orbit interaction, neutron diffraction experiments have been performed using single crystal samples of CePdSi3. There are observed magnetic reflections with incommensurate magnetic propagation vector q=(0.315,0,0) in the phase I. In addition, additional magnetic reflections were also observed in the phase III. The magnetic structure was found to be an oval-cycloidal structure at the phase III in CePdSi 3 , and we discuss the origin of the unusual magnetic structure.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Insight into Phase Transition, Electronic, Magnetic, Mechanical, and Thermodynamic Properties of TbTe: a DFT Investigation

Theoretical investigation on TbTe for its structural, electronic, magnetic, and thermodynamic stuffs has been carried within density functional theory (DFT) as implemented in WIEN2K code. TbTe was found stable in ferromagnetic phase. The calculated ground-state parameters were found in a good agreement with the experimental data. The compound was found to have a structural stability in cubic B1 (NaCl-type structure) phase, but under the application of high pressure (at 27 GPa), it undergone to B2 (CsCl-type structure) phase of pressure. The second-order elastic constants and mechanical properties like Young’s modulus, Shear modulus, Poisson ratio, Cauchy pressure (C{sub 12}–C{sub 44}), and Pugh’s ratio (B/G) were calculated. The present calculations confirmed the ductile nature of TbTe. Further, the thermodynamic investigations have been carried using quasi-harmonic Debye approximation. We have calculated the pressure and temperature dependence of Debye temperature (𝜃{sub D}), bulk modulus (B), thermal expansion (α), heat capacities (C{sub V}), and entropy (S) in the temperature range of 0 to 1000 K and pressure range of 0 to 25 GPa.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

QRPA for description of states of multiphonon origin

We propose a novel extension of the standard quasiparticle random phase approximation (QRPA) with a new form of phonon operator, which allows to describe also states of multiphonon origin. We denote this method as QRPA with non-linear phonon operator (nlQRPA) and apply it to the proton-neutron Lipkin model. We consider the simplest non-linear extension of a phonon operator where the RPA equation can be transformed into a standard form. That guarantees the orthonormality and completeness of the QRPA states of one-phonon and three-phonon origin. A rather good agreement is found both for energies and beta transition amplitudes with those obtained by a diagonalization of the schematic Hamiltonian. There is straightforward way to extend this approach also for a realistic nuclear structure calculations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Transitional Structures with Continuous Variations in Atomic Positions from Anatase to Rutile Improve Photocatalytic Activity

Abstract TiO 2 polymorphs have distinct properties that are widely employed in various applications. However, mechanisms of transformations between these polymorphs are not fully understood, especially at atomic scale, inhibiting advancing the design and application of the transitional phases. Here, based on results from semi‐in situ transmission electron microscopy, density functional theory, and X‐ray photoemission experiments, a physical picture of transitional structures is discovered, in which continuous variations in atomic positions form along a previously unreported anatase‐to‐rutile phase transformation path of [010] A –to–[] R and (004) A –to– (011) R . These gradient structures give rise to continuous band bending, which promotes electron‐hole separation and inhibits their recombination across the bulk of the particles, leading to a large functionally active volume fraction and resulting in high photoactivity. These findings suggest that interphase matter based on extended gradient structures can be designed to advance new functions not achievable using abrupt interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Rich structural phase diagram and thermoelectric properties of layered tellurides Mo{sub 1−x}Nb{sub x}Te{sub 2}

MoTe{sub 2} is a rare transition-metal ditelluride having two kinds of layered polytypes, hexagonal structure with trigonal prismatic Mo coordination and monoclinic structure with octahedral Mo coordination. The monoclinic distortion in the latter is caused by anisotropic metal-metal bonding. In this work, we have examined the Nb doping effect on both polytypes of MoTe{sub 2} and clarified a structural phase diagram for Mo{sub 1−x}Nb{sub x}Te{sub 2} containing four kinds of polytypes. A rhombohedral polytype crystallizing in polar space group has been newly identified as a high-temperature metastable phase at slightly Nb-rich composition. Considering the results of thermoelectric measurements and the first-principles calculations, the Nb ion seemingly acts as a hole dopant in the rigid band scheme. On the other hand, the significant interlayer contraction upon the Nb doping, associated with the Te p-p hybridization, is confirmed especially for the monoclinic phase, which implies a shift of the p-band energy level. The origin of the metal-metal bonding in the monoclinic structure is discussed in terms of the d electron counting and the Te p-p hybridization.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Evolution Of Lattice Structure And Chemical Composition Of The Surface Reconstruction Layer In Li1.2Ni0.2Mn0.6O2 Cathode Material For Lithium Ion Batteries

Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. Based on atomic level structural imaging, elemental mapping of the pristine and cycled samples and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions towards the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41→Spinel. For the first time, it is found that the surface facet terminated with pure cation is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for designing of cathode materials with both high capacity and voltage stability during cycling.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Intra- and intermolecular effects on the Compton profile of the ionic liquid 1,3-dimethylimidazolium chloride

We present a comprehensive simulation study on the solid-liquid phase transition of the ionic liquid 1,3-dimethylimidazolium chloride in terms of the changes in the atomic structure and their effect on the Compton profile. The structures were obtained by using ab initio molecular dynamics simulations. Chosen radial distribution functions of the liquid structure are presented and found generally to be in good agreement with previous ab initio molecular dynamics and neutron scattering studies. The main contributions to the predicted difference Compton profile are found to arise from intermolecular changes in the phase transition. This prediction can be used for interpreting future experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

First-principles investigation of Sc-III/IV under high pressure

Using an ab initio evolutionary structure prediction method in conjunction with density functional theory, we performed a systematic investigation of the structural transition of elemental scandium under pressure up to 250 GPa. Our prediction successfully reproduced several allotropes which have been reported in the literature, including the Sc-I, Sc-II, and Sc-V. Moreover, we observed a series of energetically degenerate and geometrically similar structures at 110–195 GPa, which can partly explain the experimental observations regarding the unsolved phases III and IV reported by Y. Akahama et al. [Phys. Rev. Lett. 94, 195503 (2005)]. A detailed comparison of the powder x-ray diffraction pattern suggested that the Ccca–20 phase is a likely candidate for the observed Sc-III, while Sc-IV may be explained by a structure with random stacking of two different structural units. We also used the candidate Sc-III structure as the model system to explore its superconducting behavior under pressures between 80 and 130 GPa. As a result, the predicted superconducting transition temperature Tc values are in satisfactory agreement with previous experimental results.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Lithium-cation conductivity and crystal structure of lithium diphosphate

The electrical conductivity of lithium diphosphate Li{sub 4}P{sub 2}O{sub 7} has been measured and jump-like increasing of ionic conductivity at 913 K has been found. The crystal structure of Li{sub 4}P{sub 2}O{sub 7} has been refined using high temperature neutron diffraction at 300–1050 K. At 913 K low temperature triclinic form of Li{sub 4}P{sub 2}O{sub 7} transforms into high temperature monoclinic one, space group P2{sub 1}/n, a=8.8261(4) Å, b=5.2028(4) Å, c=13.3119(2) Å, β=104.372(6)°. The migration maps of Li{sup +} cations based on experimental data implemented into program package TOPOS have been explored. It was found that lithium cations in both low- and high temperature forms of Li{sub 4}P{sub 2}O{sub 7} migrate in three dimensions. Cross sections of the migrations channels extend as the temperature rises, but at the phase transition point have a sharp growth showing a strong “crystal structure – ion conductivity” correlation. -- Graphical abstract: Crystal structure of Li{sub 4}P{sub 2}O{sub 7} at 950 K. Red balls represent oxygen atoms; black lines show Li{sup +} ion migration channels in the layers perpendicular to [001] direction. Highlights: • Structure of Li{sub 4}P{sub 2}O{sub 7} has been refined using high temperature neutron diffraction. • At 913 K triclinic form of Li{sub 4}P{sub 2}O{sub 7} transforms into high temperature monoclinic one. • The migration maps of Li{sup +} implemented into program package TOPOS have been explored. • Cross sections of the migrations channels at the phase transition have a sharp growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Disorder-induced structural transitions in topological insulating Ge-Sb-Te compounds

The mechanism for the fast switching between amorphous, metastable, and crystalline structures in chalcogenide phase-change materials has been a long-standing puzzle. Based on first-principles calculations, we study the atomic and electronic properties of metastable Ge{sub 2}Sb{sub 2}Te{sub 5} and investigate the atomic disorder to understand the transition between crystalline hexagonal and cubic structures. In addition, we study the topological insulating property embedded in these compounds and its evolution upon structural changes and atomic disorder. We also discuss the role of the surface-like states arising from the topological insulating property in the metal-insulator transition observed in the hexagonal structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units

The family of rare earth molybdenum bronzes, reduced ternary molybdates of composition LnMo{sub 16}O{sub 44,} was synthesized and a detailed structural study carried out. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with the unique isolated ReO{sub 3}-type Mo{sub 8}O{sub 36} structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μ{sub B} moments on each Mo. We suggest that the Mo{sub 8}O{sub 36} units behave like pseudoatoms with spin 1/2 derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. Interestingly, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, will be a narrow band half-metal. - Graphical abstract: LnMo{sub 16}O{sub 44} phases comprise corner sharing tetrahedral and octahedral molybdenum ions. The MoO{sub 6} octahedra form Mo{sub 8}O{sub 36} units that are well separated and act like pseudo-atoms, accommodating 11 electrons each. - Highlights: • Single crystal X-ray diffraction refinements of LnMo{sub 16}O{sub 44} single crystals for Ln=Ce, Pr, Nd, Tb, Dy and Ho. • DFT calculations based on LaMo{sub 16}O{sub 44}. • [Mo{sub 8}O{sub 36}] units behaving as superatoms with a net magnetic moment of 1 µ{sub B}. • Bronze structure containing equal number of molybdenum tetrahedra and octahedral.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Towards Accurate Predictions of Martensitic Transition Temperatures for Shape Memory Alloys from Ab Initio Simulations

Experimentally, NiTi undergoes a single martensitic phase transition around 341 K from the lowtemperature (T) monoclinic B19’ phase (P21/m) to the high-temperature cubic B2 phase (Pm3m). Theoretically, an orthorhombic B33 (Cmcm) has also been proposed as the T=0 ground state structure, although this phase has never been observed. Accurate predictions of martensitic transition temperatures (MTT) have remained elusive in part due to several well-known theoretical complexities of these systems including low temperature instabilities of the B2 phase. Recently, we proposed a rigorous thermodynamic integration approach based on ab initio simulations to resolve many of these difficulties [1,2]. However, an unsatisfying overprediction of the MTT relative to experiment (by ~100 K) means a fully quantitative theory is still lacking. In this work, we report several new developments to our method that bring first principles theory and experiment much closer into agreement. Our calculations indicate that phonon free energies at low temperature stabilizes B19’ over B33, rationalizing B19’ as the ground state down to T=0. We also find that accurate computations of the electronic free energy, i.e. the change in energy and the appearance of electronic configurational entropy due to finite temperature, is crucial to obtain accurate MTT. Incorporating these corrections results in an MTT prediction of 365 K for binary NiTi, which is in very close agreement with experiment. Our theoretical approach is expected to be a broadly applicable and predictive theory for MTT of SMAs.

Zhigang Wu↗
DOE OSTI2021

Fragile 3D Order in V 1 - x Mo x O 2

The metal-to-insulator transition in rutile VO2 has proven uniquely difficult to characterize because of the complex interplay between electron correlations and atomic structure. Here, we report the discovery of the sudden collapse of three-dimensional order in the low-temperature phase of V1-xMoxO2 at x = 0.17 and the emergence of a novel frustrated two-dimensional order at x = 0.19, with only a slight change in electronic properties. Single crystal diffuse x-ray scattering reveals that this transition from the 3D M1 phase to a 2D variant of the M2 phase results in long-range structural correlations along symmetry-equivalent (11L) planes of the tetragonal rutile structure, yet extremely short-range correlations transverse to these planes. These findings suggest that this two dimensionality results from a novel form of geometric frustration that is essentially structural in origin.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomic structure and Mott nature of the insulating charge density wave phase of 1T-TaS 2

Here, using x-ray pair distribution function (PDF) analysis and computer modeling, we explore structure models for the complex charge density wave (CDW) phases of layered 1T-TaS 2 that both well capture their atomic-level features and are amenable to electronic structure calculations. The models give the most probable position of constituent atoms in terms of 3D repetitive unit cells comprising a minimum number of Ta–S layers. Structure modeling results confirm the emergence of star-of-David (SD) like clusters of Ta atoms in the high-temperature incommensurate (IC) CDW phase and show that, contrary to the suggestions of recent studies, the low-temperature commensurate (C) CDW phase expands upon cooling thus reducing lattice strain. The C-CDW phase is also found to preserve the stacking sequence of Ta–S layers found in the room temperature, nearly commensurate (NC) CDW phase to a large extent. DFT based on the PDF refined model shows that bulk C-CDW 1T-TaS 2 also preserves the insulating state of individual layers of SD clusters, favoring the Mott physics description of the metal-to-insulator (NC-CDW to C-CDW) phase transition in 1T-TaS 2 . Our work highlights the importance of using precise crystal structure models in determining the nature of electronic phases in complex materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Regulating Anionic Redox via Mg Substitution in Mn-Rich Layered Oxide Cathodes Enabling High Electrochemical Stability for Sodium-Ion Batteries

Here, with the limited resources and high cost of lithium-ion batteries (LIBs) and the ever-increasing market demands, sodium-ion batteries (SIBs) gain much interest due to their economical sustainability, and similar chemistry and manufacturing processes to LIBs. As cathodes play a vital role in determining the energy density of SIBs, Mn-based layered oxides are promising cathodes due to their low cost, environmental friendliness, and high theoretical capacity. However, the main challenge is structural instability upon cycling at high voltage. Herein, Mg is introduced into the P2-type Na 0.62 Ni 0.25 Mn 0.75 O 2 cathode to enhance electrochemical stability. By combining electrochemical testing and material characterizations, it is found that substituting 10 mol% Mg can effectively alleviate the P2–O2 phase transition, Jahn-Teller distortion, and irreversible oxygen redox. Moreover, structural integrity is greatly improved. These lead to enhanced electrochemical performances. With the optimized sample, a remarkable capacity retention of 92% in the half cell after 100 cycles and 95% in the full cell after 170 cycles can be achieved. Altogether, this work provides an alternative way to stabilize P2-type Mn-based layer oxide cathodes, which in turn, put forward the development of this material for the next-generation SIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Gallery of soft modes: Theory and experiment at a ferromagnetic quantum phase transition

We examine the low-energy excitations in the vicinity of the quantum critical point in LiHoF4, a physical realization of the Transverse Field Ising Model, focusing on the long-range fluctuations which soften to zero energy at the ferromagnetic quantum phase transition. Microwave spectroscopy in tunable loop-gap resonator structures identifies and characterizes the electronuclear soft mode and higher-energy electronuclear states as a function of frequency and magnetic fields applied transverse and parallel to the Ising axis. These are understood in the context of a theoretical model of a soft electronuclear mode that interacts with soft photons as well as soft phonons. We identify competing infrared divergences at the quantum critical point, coming from the photons and the electronuclear soft mode. It is an incomplete cancellation of these divergences that leads to the muted but distinct signatures observed in the experiments. The application of a longitudinal magnetic field gaps the soft mode. As a result, measurements well away from the quantum critical point reveal a set of "Walker'' modes associated with ferromagnetic domain dynamics.

Dipolar interaction↗