A first-principles study on Ga stabilized δ-Pu phase stability based on structural and electronic properties
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Barman, Sajib K. (ORCID:0000000341297202)↗
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Compositional phase stability of strongly correlated electron materials within DFT+ U
Predicting the compositional phase stability of strongly correlated electron materials is an outstanding challenge in condensed matter physics. In this work, we employ the density functional theory plus U ( DFT + U ) formalism to address the effects of local correlations due to transition metal d electrons on compositional phase stability in the prototype phase stable and separating materials Li x CoO 2 and olivine Li x FePO 4 , respectively. We introduce a spectral decomposition of the DFT + U total energy, revealing the distinct roles of the filling and ordering of the d orbital correlated subspace. The on-site interaction U drives both of these very different materials systems towards phase separation, stemming from enhanced ordering of the d orbital occupancies in the x = 0 and x = 1 species, whereas changes in the overall filling of the d shell contribute negligibly. We show that DFT + U formation energies are qualitatively consistent with experiments for phase stable Li x CoO 2 , phase separating Li x FePO 4 , and phase stable Li x CoPO 4 . However, we find that charge ordering plays a critical role in the energetics at intermediate x , strongly dampening the tendency for the Hubbard U to drive phase separation. Most relevantly, the phase stability of Li 1 / 2 CoO 2 within DFT + U is qualitatively incorrect without allowing charge ordering, which is problematic given that neither charge ordering nor the band gap that it induces are observed in experiment. We demonstrate that charge ordering arises from the correlated subspace interaction energy as opposed to the double counting. Additionally, we predict the Li order-disorder transition temperature for Li 1 / 2 CoO 2 , demonstrating that the unphysical charge ordering within DFT + U renders the method problematic, often producing unrealistically large results. Overall, our findings motivate the need for other advanced techniques, such as DFT plus dynamical mean-field theory, for total energies in strongly correlated materials.
36 MATERIALS SCIENCE↗
Compositional phase stability of correlated electron materials within DFT+DMFT
Predicting the compositional phase stability of strongly correlated electron materials is an outstanding challenge in condensed matter physics, requiring precise computations of total energies. In this work, we employ the density functional theory plus dynamical mean-field theory (DFT+DMFT) formalism to address local correlations due to transition metal $\textit{d}$ electrons on compositional phase stability in the prototype rechargeable battery cathode material Li x CoO 2 , and detailed comparisons are made with the simpler DFT+$\textit{U}$ approach (i.e., the Hartree-Fock solution of the DMFT impurity problem). Local interactions are found to strongly impact the energetics of the band insulator LiCoO 2 , most significantly via the $E_g$ orbitals, which are partially occupied via hybridization with $\textit{O p}$ states. We find CoO 2 and Li 1/2 CoO 2 to be moderately correlated Fermi liquids with quasiparticle weights of 0.6–0.8 for the $T_{2g}$ states, which are most impacted by the interactions. Further, as compared to DFT+$\textit{U}$, DFT+DMFT considerably dampens the increase in total energy as $\textit{U}$ is increased, which indicates that dynamical correlations are important to describe this class of materials despite the relatively modest quasiparticle weights. Unlike DFT+$\textit{U}$, which can incorrectly drive Li x CoO 2 toward spurious phase separating or charge-ordered states, DFT+DMFT correctly captures the system's phase stability and does not exhibit a strong charge-ordering tendency. Most importantly, the error within DFT+$\textit{U}$ varies strongly as the composition changes, challenging the common practice of artificially tuning $\textit{U}$ within DFT+$\textit{U}$ to compensate the errors of Hartree-Fock. DFT+DMFT predicts the average intercalation voltage decreases relative to DFT, opposite to the result of DFT+$\textit{U}$, which would yield favorable agreement with experiment in conjunction with the overprediction of the voltage by the strongly constrained and appropriately normed DFT functional.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Resolving phase stability in the Ti-O binary with first-principles statistical mechanics methods
The Ti-O system consists of a multitude of stable and metastable oxides that are used in wide ranging applications. In this work we investigate phase stability in the Ti-O binary from first principles. We perform a systematic search for ground state structures as a function of oxygen concentration by considering oxygen-vacancy and/or titanium-vacancy orderings over four parent crystal structures: (i) hcp Ti, (ii) ω-Ti, (iii) rocksalt, and (iv) hcp oxygen containing interstitial titanium. We explore phase stability at finite temperature using cluster expansion Hamiltonians and Monte Carlo simulations. The calculations predict a high oxygen solubility in hcp Ti and the stability of suboxide phases that undergo order-disorder transitions upon heating. Vacancy ordered rocksalt phases are also predicted at low temperature that disorder to form an extended solid solution at high temperatures. Predicted stable and metastable phase diagrams are qualitatively consistent with experimental observations, however, important discrepancies are revealed between first-principles density functional theory predictions of phase stability and the current understanding of phase stability in this system.
36 MATERIALS SCIENCE↗
The relationship between phase stability and frequency stability and a method of converting between them
A method is presented for obtaining the value of the phase stability from time domain frequency stability measurements. Definition of frequency and phase stability are presented. The various types of noise sources in an oscillator and how their location in the oscillator circuitry determines the resultant phase and frequency noise spectrum are described. With this knowledge, the type of noise spectrum from time domain frequency stability measurements is determined. Using certain conversions, the total phase noise spectrum is obtained, which is integrated to obtain the phase stability. Examples of the conversion process are also presented.
Bohn, P. P.↗
Enhanced Phase Stability of Sm 2 (Fe, Al) 17 C x
Aluminum doping can improve the phase stability of metastable compound Sm 2 Fe 17 C x with a high carbon content (x > 1.5). We investigated the preferential site substitution of Al, chemical bonding, and structural stability in Sm 2 (Fe,Al) 17 C 3 using first-principle calculations. Our results reveal a strong correlation between the preferential substitution of Fe by Al and the atomic site chemical environment, which affects the overall phase stability. Specifically, Al preferentially occupies the 9d site in Sm 2 (Fe,Al) 17 C 3 . At the same time, Al prefers the site 6c in its parent phase Sm 2 (Fe,Al) 17 . Partial replacement of Fe with Al leads to a more negative formation energy, indicating enhanced thermodynamic stability. Crystal Orbital Hamilton Population (COHP) and Crystal Orbital Bond Index (COBI) analysis suggest that insertion of carbon weakens the bonding strength of Sm-Fe (18f) and Sm-Fe (18h), resulting in metastability of Sm 2 Fe 17 C x . Doping Al strengthens Al-Fe, Al-Sm, Sm-Fe (18f, 18h) and Fe–C bonding in Sm 2 (Fe,Al) 17 C 3 , as revealed by calculated COHP and COBI. These effects contribute to improved phase stability in the Al-doped 2:17 interstitial compound.
chemical bonding↗
Chemical bonding, phase stability and magnetic property in Sm 2 Fe 17 X 3 (X=H, C, N): A first-principles perspective
As a promising alternative to Nd–Fe–B magnets, the critical rare earth free Sm 2 Fe 17 X 3 (X = C, N) exhibits potential for high-performance magnets. However, their poor phase stability remains a major obstacle to developing bulk magnets. We investigated the phase stability and intrinsic magnetic properties of Sm 2 Fe 17 X 3 (X = H, C, N) using first-principles calculations and chemical bond analysis. The formation energies are negative, while the decomposition energies are −1.53, 0.348, and −0.74 eV per formula unit for X = H, C, and N, respectively, which is responsible for the weak thermal stability. Our chemical bond analysis reveals that the bonding asymmetry between Sm–X and Fe–X interactions creates local structural distortions and degrades the phase stability of Sm 2 Fe 17 X 3 . The project Crystal Orbital Hamilton Population (-pCOHP) analysis indicates that the Sm–X bonding remains positive up to the Fermi level, indicating stable bonding interactions. Here, in contrast, the Fe–X bonding becomes negative near the Fermi level, signifying anti-bonding contributions that reduce structural stability. Interstitial atoms X expand the lattice and enhance Fe magnetic moments, but Fe–X bonding suppresses neighboring Fe moments. Electron transfer from Sm to X modifies the valence state of Sm and the crystal field at the site, contributing to enhanced magnetocrystalline anisotropy in Sm 2 Fe 17 X 3 . Among the interstitial elements, carbon and nitrogen—with their larger atomic radius and higher electronegativity—induce greater lattice expansion and form stronger bonds with neighboring Sm and Fe atoms compared to hydrogen. Consequently, Sm 2 Fe 17 X 3 (X = C and N) exhibits better phase stability and significant improvement in magnetic properties.
Chemical bonding↗
Comparison between thermochemical and phase stability data for the quartz-coesite-stishovite transformations
Phase stability and elasticity data have been used to calculate the Gibbs free energy, enthalpy, and entropy changes at 298 K and 1 bar associated with the quartz-coesite and coesite-stishovite transformations in the system SiO2. For the quartz-coesite transformation, these changes disagree by a factor of two or three with those obtained by calorimetric techniques. The phase boundary for this transformation appears to be well determined by experiment; the discrepancy, therefore, suggests that the calorimetric data for coesite are in error. Although the calorimetric and phase stability data for the coesite-stishovite transformation yield the same transition pressure at 298 K, the phase-boundary slopes disagree by a factor of two. At present, it is not possible to determine which of the data are in error. Thus serious inconsistencies exist in the thermodynamic data for the polymorphic transformations of silica.
Weaver, J. S.↗
Theoretical perspective on phase stability and polarization switching in ferroelectric hafnia
Fluorite-based ferroelectric materials are revolutionizing the application space of polar semiconductors. These materials leverage robust polarization of extremely thin films, compatibility with the silicon chip processing, and decades of manufacturing experience to enable a new generation of ferroelectric memory devices. As a new paradigm for ferroelectrics, understanding of phase transitions and the switching mechanism in fluorites is essential both for advancing applications and for fundamental science. In this article, we outline the recent progress that has been made to understand the relative phase stability, phase transition and order parameter coupling, ferroelectric switching through unique nucleation and growth processes, and how defects affect these phases and processes. The main challenges, opportunities, and next steps for leveraging these materials for next-generation devices are reviewed.
Condensed Matter Physics↗
Structural damage and phase stability of Al 0.3 CoCrFeNi high entropy alloy under high temperature ion irradiation
In this study, an initially single phase high entropy alloy (HEA) Al 0.3 CoCrFeNi was irradiated by 3 MeV Au ions to a fluence of 6 × 10 15 cm –2 (~31 dpa at damage peak) at four different temperatures ranging from 250 °C to 650 °C. Transmission electron microscopy (TEM) and Atom probe tomography (APT) were employed to study the evolution of structural damage and phase stability with irradiation temperature. Al 0.3 CoCrFeNi exhibited a similar evolution of irradiation-induced defects with temperature as compared with conventional FCC alloys. At 250 °C and 350 °C, most of the visible irradiation-induced defects were faulted 1/3$\langle{111}\rangle$ dislocation loops. As the irradiation temperature increased to 500 °C, perfect 1/2$\langle{110}\rangle$ dislocation loops were observed along with the faulted loops. At the highest irradiation temperature 650 °C, only dislocation lines and networks could be observed. Regarding phase stability, the 3 MeV Au irradiation was observed to suppress the precipitation of (Ni, Al)-enriched nano clusters and the L12 ordered structure at irradiation temperatures 250 °C to 500 °C whereas precipitation of the B2 ordered structure was accelerated at 650 °C. This resulted in qualitatively opposite precipitation behavior between the ion irradiated damage region and unirradiated region at 500 °C and 650 °C. The opposite phase stability of the ion-irradiated damage region and unirradiated region at different temperatures is attributed to the competing effects of ballistic dissolution vs irradiation enhanced diffusion on precipitation.
36 MATERIALS SCIENCE↗
Phase stability and transformation in a light-weight high-entropy alloy
Light-weight high-entropy alloys (HEAs) with a vast alloy-design space have offered new avenues to explore novel low-cost, high strength-to-weight ratio structural materials. Studying their phase stability and possible transformations is critical for designing microstructures for optimal material properties. However, the complex local atomic environment of HEAs poses challenges to the fundamental understanding of phase stability and transformation behaviors. The present paper investigates the phase stability and transformation behaviors of a newly-designed light-weight Al 1.5 CrFeMnTi HEA by integrated experimental and theoretical approaches. The coherent precipitation of the L2 1 phase within the body-centered-cubic (BCC) matrix at intermediate temperatures was observed, and the size, shape, coherency, and spatial distribution of the L2 1 phase were subsequently altered through selected annealing treatments. Moreover, the CALculation of PHAse Diagrams (CALPHAD) and first-principle calculations successfully optimize the compositions of light-weight HEAs with a coherent BCC/L2 1 two-phase structure. Finally, shed light by the present study, novel light-weight HEAs, featuring the lower density (below 6 g/cm 3 ) and cost, can be designed for high-temperature applications.
36 MATERIALS SCIENCE↗
Improved phase stability of formamidinium lead triiodide perovskite by strain relaxation
Though formamidinium lead triiodide (FAPbI 3 ) possesses a suitable band gap and good thermal stability, the phase transition from the pure black perovskite phase (α-phase) to the undesirable yellow nonperovskite polymorph (δ-phase) at room temperature, especially under humid air, hinders its practical application. Here, we investigate the intrinsic instability mechanism of the α-phase at ambient temperature and demonstrate the existence of an anisotropic strained lattice in the (111) plane that drives phase transformation into the δ-phase. Methylammonium bromide (MABr) alloying (or FAPbI 3 -MABr) was found to cause lattice contraction, thereby balancing the lattice strain. This led to dramatic improvement in the stability of α-FAPbI 3 . As a result, solar cells fabricated using FAPbI 3 -MABr demonstrated significantly enhanced stability under the humid air.
14 SOLAR ENERGY↗
Low-Density Parity-Check Stabilizer Codes as Gapped Quantum Phases: Stability under Graph-Local Perturbations
We generalize the proof of stability of topological order, due to Bravyi, Hastings, and Michalakis, to stabilizer Hamiltonians corresponding to low-density parity-check (LDPC) codes without the restriction of geometric locality in Euclidean space. We consider Hamiltonians 𝐻 0 defined by ⟦𝑁,𝐾,𝑑⟧ LDPC codes, which obey certain topological quantum order conditions: (i) code distance 𝑑 ≥ 𝑐log (𝑁), implying local indistinguishability of ground states, and (ii) a mild condition on local and global compatibility of ground states—these include good quantum LDPC codes and the toric code on a hyperbolic lattice, among others. We consider stability under weak perturbations that are quasilocal on the interaction graph defined by 𝐻 0 and that can be represented as sums of bounded-norm terms. As long as the local perturbation strength is smaller than a finite constant, we show that the perturbed Hamiltonian has well-defined spectral bands originating from the 𝑂(1) smallest eigenvalues of 𝐻 0 . The band originating from the smallest eigenvalue has 2 𝐾 states, is separated from the rest of the spectrum by a finite energy gap, and has exponentially narrow bandwidth 𝛿 =𝐶𝑁𝑒 −Θ(𝑑) , which is tighter than the best-known bounds even in the Euclidean case. We also obtain that the new ground-state subspace is related to the initial-code subspace by a quasilocal unitary, allowing one to relate their physical properties. Our proof uses an iterative procedure that performs successive rotations to eliminate non-frustration-free terms in the Hamiltonian. Our results extend to quantum Hamiltonians built from classical LDPC codes, which give rise to stable symmetry-breaking phases. These results show that LDPC codes very generally define stable gapped quantum phases, even in the non-Euclidean setting, initiating a systematic study of such phases of matter.
mathematical physics↗
Investigating the role of phonons in the phase stability of uranium-based Laves phases
DFT investigations of the thermodynamic stability of UCo 2 and UNi 2 for three Laves phase structure types were extrapolated to UCo 2 x Ni 2(1− x ) .
36 MATERIALS SCIENCE↗
Phase stabilized homodyne of infrared scattering type scanning near-field optical microscopy
Scattering type scanning near-field optical microscopy (s-SNOM) allows sub diffraction limited spatial resolution. Interferometric homodyne detection in s-SNOM can amplify the signal and extract vibrational responses based on sample absorption. A stable reference phase is required for a high quality homodyne-detected near-field signal. This work presents the development of a phase stabilization mechanism for s-SNOM to provide stable homodyne conditions. The phase stability is found to be better than 0.05 rad for the mid infrared light source. Phase stabilization results in improved near field images and vibrational spectroscopies. Spatial inhomogeneities of the boron nitride nanotubes are measured and compared.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
High Entropy Ceramics: Compositionally Predicted Phase Stability and Mechanical Shock Induced Phase Transformations
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Lowry, Daniel Robert↗
Understanding phase stability of Al-Co-Cr-Fe-Ni high entropy alloys
The concept of high entropy alloy (HEA) opens a vast unexplored composition range for alloy design. As a well-studied system, Al-Co-Cr-Fe-Ni has attracted tremendous amount of attention to develop new-generation low-density structural materials for automobile and aerospace applications. In spite of intensive investigations in the past few years, the phase stability within this HEA system is still poorly understood and needs to be clarified, which poses obstacles to the discovery of promising Al-Co-Cr-Fe-Ni HEAs. In the present work, the CALPHAD approach is employed to understand the phase stability and explore the phase transformation within the Al-Co-Cr-Fe-Ni system. As a result, the phase-stability mapping coupled with density contours is then constructed within the composition - temperature space, which provides useful guidelines for the design of low-density Al-Co-Cr-Fe-Ni HEAs with desirable properties.
36 MATERIALS SCIENCE↗
Variation of γ′ Formers and Refractory Elements for Enhanced Creep resistance and Phase Stability of HAYNES® 282® Alloy
Modifications to the chemistry of alloy 282 were performed to improve the alloy’s resistance to long term creep deformation as well as phase stability. Alloys were prepared using vacuum induction melting, computationally optimized homogenization heat treatment and hot working. Phase stability studies were carried out for up to 5,000 hours at 800°C and 900°C while creep testing was performed at conditions leading to lives past 7,000 hours for temperatures ranging from 740°C to 900°C. The formation of σ and μ phases were reduced in the modified alloy. Atom probe tomography (APT) was performed on the specimens from the phase stability study to investigate changes in the elemental partitioning to the γ and γ′ phases. Post deformation microstructures were analyzed using EBSD and TEM to study the influence of the detrimental phases on damage accumulation during creep.
Detrois, Martin↗