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At least 289 records · Page 16

Validating first-principles phonon lifetimes via inelastic neutron scattering

Phonon lifetimes are a key component of quasiparticle theories of transport; yet first-principles lifetimes are rarely directly compared with inelastic neutron scattering (INS) results. Existing comparisons show discrepancies even at temperatures where perturbation theory is expected to be reliable. In this paper, we demonstrate that the reciprocal space voxel (q voxel), which is the finite region in reciprocal space required in INS data analysis, must be explicitly accounted for within theory in order to draw a meaningful comparison. Here, we demonstrate accurate predictions of peak widths of the scattering function when accounting for the q voxel in CaF 2 and ThO 2 . Passing this test implies high fidelity of the phonon interactions and the approximations used to compute the Green's function, serving as a critical benchmark of theory and indicating that other material properties should be accurately predicted, which we demonstrate for thermal conductivity.

36 MATERIALS SCIENCE↗

First-principles equations of state and structures of liquid metals in multi-megabar conditions

Liquid metals at extreme pressures and temperatures are widely interested in the high-pressure community. Based on density functional theory molecular dynamics, we conduct first-principles investigations on the equation of state ( EOS) and structures of four metals (Cu, Fe, Pb, and Sn) at 1.5–5 megabar conditions and 5 × 10 3 –4 × 10 4 K. Our first-principles EOS data enable evaluating the performance of four EOS models in predicting Hugoniot densities and temperatures of the four systems. We find the melting temperature of Cu is 1000–2000 K higher and shows a similar Clapeyron slope, in comparison to those of Fe. Our structure, coordination number, and diffusivity analysis indicates all the four liquid metals form similar simple close-packed structures. Our results set theoretical benchmarks for EOS development and structures of metals in their liquid states and under dynamic compression.

36 MATERIALS SCIENCE↗

First-principles investigation of phase stability in layered Na x ⁢CrO 2

Layered oxide intercalation compounds continue to attract interest as electrode materials for Na-ion batteries. However, many of these materials undergo complex phase transitions during cycling that influence battery performance but are still not completely understood. We have conducted a first-principles study of layered Na x ⁢CrO 2 (0 ≤ x ≤ 1) to assess phase stability between various Na-vacancy ordered phases in the O3 and P3 host structures. We predict that many of the low-energy phases belong to families of Na orderings that follow specific patterns. At high x, we identify families of vacancy row orderings in O3, which may also couple to magnetic orderings of the Cr spins. We predict similar orderings at intermediate x in P3 that contain antiphase boundaries between regions of the x = 1/2 ordering. In both cases, the average spacing between rows/boundaries is set by the overall composition. At x = 0, we find a strong preference for charge disproportionation and migration of Cr to tetrahedral sites in the intercalation layers. Finally, we obtain generally good agreement with experimental observations and rationalize key discrepancies.

25 ENERGY STORAGE↗

Thermodynamic modeling of the Pd–Zn system with uncertainty quantification and its implication to tailor catalysts

Pd–Zn intermetallic catalysts show encouraging combinations of activity and selectivity on well-defined active site ensembles. Thermodynamic description of the Pd–Zn system, delineating phase boundaries and enumerating site occupancies within intermediate alloy phases, is essential to determining the ensembles of Pd–Zn atoms as a function of composition and temperature. Combining the present extensive first-principles calculations based on density functional theory (DFT) and available experimental data, the Pd–Zn system was remodeled using the CALculation of PHAse Diagrams (CALPHAD) approach. High throughput modeling tools with uncertainty quantification, i.e., ESPEI and PyCalphad, were incorporated in the phase analysis. Here, the site occupancies across the γ phase composition region were given special attention. A four-sublattice model was used for the γ phase owing to its four Wyckoff positions, i.e., the outer tetrahedral (OT) site 8c, the inner tetrahedral (IT) site 8c, the octahedral (OH) site 12e, and the cuboctahedral (CO) site 24g. The site fractions of Pd and Zn calculated from the present thermodynamic model show the occupancy preference of Pd in the OT and OH sublattices in agreement with experimental observations. The force constants obtained from DFT-based phonon calculations further supports the tendency of Pd occupying the OH sublattice compared with the IT and CO sublattice. The catalytic ensembles changing from Pd monomers (Pd 1 ) to trimers (Pd 3 ) on the surface of γ phase are attributed to the increase of Pd occupancy in the OH sublattice.

36 MATERIALS SCIENCE↗

First-principles derivation of magnetic interactions in the triangular quantum spin liquid candidates KYb C h 2 ( C h = S , Se , Te ) and A YbSe 2 ( A = Na , Rb )

The AYb Ch 2 (A=alkali metal, Ch=chalcogen) delafossites are a family of crystals which have a triangular lattice of effective S=1/2 moments on their Yb atoms. They hold great promise for the realization of the triangular quantum spin liquid state because of their defect-minimized growth and the ability to interchange chemical constituencies among the family. Here we use ab initio computations to evaluate the exchange couplings of four realized (and one theoretical) rhombohedral delafossite structures and examine the influence of chemical substitution on promoting the development of a quantum spin liquid state. We find good agreement with experiment regarding the antiferromagnetic nearest-neighbor exchange J 1 , but our calculations underestimate J 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

First-principles molten salt phase diagrams through thermodynamic integration

Precise prediction of phase diagrams in molecular dynamics simulations is challenging due to the simultaneous need for long time and large length scales and accurate interatomic potentials. Here, we show that thermodynamic integration from low-cost force fields to neural network potentials trained using density-functional theory (DFT) enables rapid first-principles prediction of the solid–liquid phase boundary in the model salt NaCl. We use this technique to compare the accuracy of several DFT exchange–correlation functionals for predicting the NaCl phase boundary and find that the inclusion of dispersion interactions is critical to obtain good agreement with experiment. Importantly, our approach introduces a method to predict solid–liquid phase boundaries for any material at an ab initio level of accuracy, with the majority of the computational cost at the level of classical potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Complex fermiology and electronic structure of antiferromagnet EuSnP

Throughout this work, we studied the electronic structure of a layered antiferromagnetic metal, EuSnP, in the paramagnetic and in the antiferromagnetic phase using angle-resolved photoemission spectroscopy (ARPES) alongside density-functional theory (DFT)-based first-principles calculations. The temperature dependence of the magnetic susceptibility measurements exhibits an antiferromagnetic transition at a Néel temperature of 21 K. Employing high-resolution ARPES, the valence-band structure was measured at several temperatures above and below the Néel temperature, which produced identical spectra independent of temperature. Through analysis of the ARPES results presented here, we attribute the temperature-independent spectra to the weak coupling of the Sn and P conduction electrons with Eu 4⁢ƒ states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermodynamic properties of the Nd-Bi system via emf measurements, $\mathrm{DFT}$ calculations, machine learning, and $\mathrm{CALPHAD}$ modeling

Thermodynamic properties of the Nd-Bi system were investigated using a combination of experimental measurements, first-principles calculations based on density functional theory (DFT), data mining and machine learning (DM + ML) predictions, and calculation of phase diagrams (CALPHAD) modeling. The electromotive force (emf) of Nd-Bi alloys in molten LiCl-KCl-NdCl 3 at 773–973 K was measured via coulometric titration of Nd into Bi for the determination of thermochemical properties such as activity coefficients and solubilities of Nd in Bi. A new peritectic reaction of [liquid + NdBi 2 = Nd 3 Bi 7 ] at 774 K was confirmed using differential scanning calorimetry, structural (X-ray diffraction), and microstructural (scanning electron microscopy) analyses. The unknown crystal structure of NdBi2 was suggested to be a mixture of the anti-La 2 Sb configuration and the La 2 Te-type configuration based on ML predictions for over 26,000 data-mined AB 2 -type configurations together with DFT-based verifications. Using the newly acquired experimental data and DFT-based calculations, the thermodynamic description of the Nd-Bi system was remodeled, and a more complete Nd-Bi phase diagram was calculated, including the Nd 3 Bi 7 compound, invariant transition reactions, and liquidus temperatures.

36 MATERIALS SCIENCE↗

A Multi-Scale Computational Platform for Predictive Modeling of Corrosion in Al-Steel Joints (Final Report)

The research team proposed to develop innovative multi-scale models to predict corrosion and the resulting mechanical performances in aluminum-steel joints. The methods of joining considered are resistance spot welding, self-piercing riveting, and rivet-welding, all suitable for mass production applications. The multi-scale models integrate high throughput first-principle calculations based on density functional theory (DFT), high throughput calculation of phase diagrams (CALPHAD) modeling, and finite element method (FEM) simulations. These models are to be validated through laboratory experiments. Furthermore, the models are available as open source so as to enable scientists and engineers in the community to adapt and contribute to the development and application. The approaches rely on the research team’s extensive experience on the prediction of properties of individual phases at finite temperatures and variable compositions through DFT calculations, and our broad expertise on dissimilar material joining and their corrosion. The proposed computational framework enables high throughput computations for improved predictions of corrosion and the associated mechanical performance in dissimilar material joints, resulting in significant reduction in computational time needed by the current state-of-the-art methods. With the participation of researchers from three universities, an auto manufacturer, two manufacturing technology/equipment suppliers, and a software developer/vendor, the interdisciplinary research team applies the technical development on both phase-based modeling and laboratory experiments into the automobile body joining processes for validation and technology demonstration. The global cost of corrosion was estimated at about 3.4% of the global GDP in 2013. By using available corrosion control practices, it is estimated a saving between 15-35% of the cost of corrosion. In the U.S., more than $276 billion is spent repairing corrosion damage. Prediction of the corrosion and its impact on performance of the dissimilar material joints is critical for reducing the massive number of the current corrosion-based recalls for automobiles. Thus, the project goal is to develop models to enable predictive maintenance and end-of-life planning of multi-metal joints with risk of corrosion under different conditions such as exposure to high temperatures in summer and salt solutions in winter, quantified through its pH. An academia-industry consortium led by the University of Michigan and including Pennsylvania State University, University of Illinois Urbana-Champaign, University of Georgia, General Motors Company, Livermore Software Technology Corporation, and Optimal Process Technologies, LLC. created multi-scale models for prediction of corrosion in aluminum-steel joint structures such of them used in vehicle subassemblies – chassis and transmission systems. Starting from the first principle calculations, the team developed mathematical and data-driven models to predict the metallic components, which are formed during joining of two metals, for example aluminum and steel - a lightweight multilateral system which is currently used in more than 60% car bodies. These models were used for simulating chemical reactions that are happening when the joining metallic components are exposed to high temperatures and different pH values. The team was able to predict how the corrosion installs on the metallic components and how they lead to a sudden failure of components in cars. Newly developed machine learning algorithms combining Science, Technology, Engineering and Math disciplines, advanced finite element simulation and experimental validations have been integrated in a platform for prediction of the corrosion evolution and prediction the failure of joints under mechanical loadings and fatigue. Moreover, based on machine learning and inverse analysis, the team proposed solutions for designing new metallic alloys less susceptible to corrosion when joining multi-material assembles. An average of 4% error compared with experiments was achieved for the most common joints that are used in vehicle subassemblies.

36 MATERIALS SCIENCE↗

Unraveling the transformation pathway of the 𝛽 to 𝛾 phase transition in Ga 2 ⁢O 3 from atomistic simulations

Defect spinel 𝛾−Ga 2 ⁢O 3 is the least stable polymorph of Ga 2 ⁢O 3 , so its frequent appearance as a structural defect within or on the surface of monoclinic 𝛽−Ga 2 ⁢O 3 remains a mystery. Through first-principles calculations, we explore potential pathways for the phase transition from 𝛽−Ga 2⁢ O 3 to 𝛾−Ga 2 ⁢O 3 , and examine two key driving forces: tensile strain and Ga deficiency. When configurational entropy contributions to phase energies are included, the 𝛾 phase becomes energetically competitive with the 𝛽 phase, with the free energy difference between these phases diminishing even further under Ga-deficient conditions. Notably, a stability crossover occurs at room temperature at high vacancy concentrations ([V$^{3−}_{Ga}$]>3%) . A simple model 𝛽 → 𝛾 transformation pathway is identified, comprising two primary reactions, that enables the formation of the 𝛾 phase via simultaneous migration of Ga atoms from tetrahedral lattice sites to octahedral interstitial positions. The transformation barriers are prohibitively large in pristine Ga 2 ⁢O 3 , but can be substantially reduced by: (1) the presence of Ga vacancies, (2) elongational strains along the crystallographic 𝑎-axis, and (3) when volumetric relaxations are possible during transformation. These results elucidate prior experimental observations, where 𝛾−Ga 2⁢ O 3 is seen on damaged surfaces or in highly 𝑛-type 𝛽−Ga 2⁢ O 3 environments, which support Ga deficiency and mechanical strain. The insights into the driving forces and mechanisms of 𝛾−Ga 2⁢ O 3 formation enhance understanding of how localized strain and nonequilibrium defect concentrations may facilitate its formation from the 𝛽 phase.

Defects↗

Engineering 2D Square Lattice Hubbard Models in 90° Twisted GeX/SnX (X =S, Se) Moiré Superlattices

Because of the large-period superlattices emerging in moiré two-dimensional (2D) materials, electronic states in such systems exhibit low energy flat bands that can be used to simulate strongly correlated physics in a highly tunable setup. While many investigations have thus far focused on moiré flat bands and emergent correlated electron physics in triangular, honeycomb, and quasi-one-dimensional lattices, tunable moiré realizations of square lattices subject to strong correlations remain elusive. Here, in this work, we propose a feasible scheme to construct moiré square lattice systems by twisting two or more layers of 2D materials in a rectangular lattice by 90°. We demonstrate the concept with twisted GeX/SnX (X =S, Se) moiré superlattices and calculate their electronic structures from first principles. We show that the lowest conduction flat band in these systems can be described by a square lattice Hubbard model with parameters which can be controlled by varying the choice of host materials, number of layers, and external electric fields. In particular, twisted double bilayer GeSe realizes a square lattice Hubbard model with strong frustration due to the next-nearest-neighbor hopping that could host unconventional superconductivity, in close analogy to the Hubbard model for copper-oxygen planes of cuprate high-temperature superconductors. The presented scheme uses 90° twisted 2D materials with rectangular unit cells as a promising platform for realizing the physical phenomena of square lattice Hubbard models, establishing a new route for studying its rich phase diagram of magnetism, charge order, and unconventional superconductivity in a highly tunable setting.

2-dimensional systems↗

2p x-ray absorption spectroscopy of 3d transition metal systems

This review provides an overview of the different methods and computer codes that are used to interpret 2p x-ray absorption spectra of 3d transition metal ions. We first introduce the basic parameters and give an overview of the methods used. We start with the semi-empirical multiplet codes and compare the different codes that are available. A special chapter is devoted to the user friendly interfaces that have been written on the basis of these codes. Next we discuss the first principle codes based on band structure, including a chapter on Density Functional theory based approaches. We also give an overview of the first-principle multiplet codes that start from a cluster calculation and we discuss the wavefunction based methods, including multi-reference methods. We end the review with a discussion of the link between theory and experiment and discuss the open issues in the spectral analysis.

36 MATERIALS SCIENCE↗

Effect of XC functionals and dispersion corrections on the DFT‐computed structural and vibrational properties of SrCl 2 –NaCl and ZrF 4 –LiF

Density functional theory (DFT) calculations were performed to examine the impact of exchange–correlation (XC) functionals and van der Waals corrections (specifically the D3 method) on the structural and vibrational properties of the SrCl 2 –NaCl and ZrF 4 –LiF salt systems. Multiple XC functionals, including the local density approximation (LDA), the generalized gradient approximation using the Perdew–Burke–Ernzerhof (PBE) model, and its modified form suitable for solids (PBEsol), the dispersion-corrected PBE-D3 and PBEsol-D3, were considered. Of these functionals, LDA was found to exhibit the highest degree of error, while PBEsol and PBE-D3 displayed the least error. Underestimated lattice parameters compared with experimental values were observed to result in higher force constants, leading to an overprediction of vibrational frequencies. Conversely, an overestimation of lattice parameters was associated with lower vibrational frequencies. The methodology presented in this study yielded results that are in good agreement with experiment, irrespective of the method (finite differences vs. density functional perturbation theory) employed for calculating infrared and Raman spectra. It was further demonstrated that for alkali halides with weak Raman scattering, utilizing a supercell constructed from primitive cells better predicts Raman features than does the use of conventional cells.

Raman↗

Speciation and diffusive dynamics in hydrated grain boundaries of complex oxide Gd2Ti2O7

Abstract Grain boundaries in polycrystalline materials significantly affect their properties, such as ionic transport, corrosion, and chemical durability. The pyrochlore compound (Gd 2 Ti 2 O 7 ) is employed as a model for complex oxides and is known for its diverse applications, including nuclear waste immobilization. Density functional theory-based first-principles molecular dynamics simulations were performed at different temperatures on the hydrated grain boundary system. The results show extensive transformations within the grain boundaries among hydrous water species (OH − , H 2 O, and H 3 O + ). The temperature dependence of self-diffusion coefficients follows Arrhenius behavior, with an activation energy of 35.9 kJ/mol for hydrogen and 46.3 kJ/mol for oxygen. The lifetime of OH − is about three to four times longer than that of H 2 O at temperatures from 800 to 2100 K, suggesting the greater stability of OH − over H 2 O, a unique characteristic of the grain boundaries. The estimated lifetime of the hydrous species decreases as the temperature increases, with an activation energy of 9.9 kJ/mol for OH − and 13.4 kJ/mol for H 2 O. While Gd 3 + is more mobile than Ti 4+ , both the Gd 3 + and Ti 4+ cations are orders of magnitude less mobile than the water species. The results suggest that water species are much more mobile within grain boundaries than in the bulk crystal and have the potential to penetrate deep into polycrystalline materials through grain boundaries, leading to grain boundary degradation and dissolution. The different mobilities of cations in complex oxides can lead to leaching of certain cations and incongruent dissolution during the chemical weathering of Earth and industrial materials.

B. Ghosh, Dipta↗

The potential application of VS 2 as an electrode material for Mg ion battery: A DFT study

Herein, by means of first-principle calculations based on density functional theory (DFT), the electrochemical properties of monolayer VS 2 (M-VS 2 ), double-layer VS 2 (D-VS 2 ) and bulk VS 2 (B-VS 2 ) as electrode materials for Mg-ion batteries (MIBs) were comprehensively explored. The computation results reveal that Mg atom can strongly bind with the three different forms of VS 2 . All of the Mg adsorbed VS 2 systems demonstrate metallic characteristics, which indicates a good electronic conductivity. In addition, crystal orbital hamiltonian population shows that the stability of V-S bond is weakened after adsorption of Mg atom. The low diffusion barriers of Mg give rise to the high rate performance of VS 2 in MIBs. More interestingly, the three types of VS 2 display same storage ability for Mg cations, which can adsorb 0.5 Mg atoms for VS 2 , producing maximum theoretical capacity 233 mA h g -1 for MIBs. Furthermore, the average working voltages results suggest that M-VS 2 can be employed as anode materials, while D-VS 2 , B-VS 2 can be used as cathode materials for MIBs.

25 ENERGY STORAGE↗

Thermodynamic re-modeling of the Yb-Sb system aided by first-principles calculations

Here, the thermodynamic description of the Yb-Sb binary system is developed by means of the CALculations of PHAse Diagrams (CALPHAD) method by combining experimental data in the literature and predictions from first-principles calculations based on density functional theory (DFT) in the literature and the present work. Two pseudopotentials of Yb are compared in the present DFT-based calculations with 14 and 13 f-electrons frozen in the core, i.e., 5p 6 6s 2 and 5p 6 6s 2 5 d 1 electrons as valence electrons, termed Yb_2 and Yb_3, respectively. It is shown that the phonon spectrum of the YbSb phase calculated using the Yb_3 pseudopotential does not have imaginary phonon modes and is subsequently used to predict its temperature dependent thermodynamic properties by the DFT-based quasiharmonic phonon calculations. The present thermodynamic database includes the Yb 16 Sb 11 phase in addition to five intermetallic phases that were considered in previous modeling studies, i.e., YbSb 2 , YbSb, Yb 11 Sb 10 , Yb 4 Sb 3 , and Yb 5 Sb 3 . The high temperature orthorhombic structure of the Yb 5 Sb 3 phase is not considered in the present work as it was stabilized by hydrogen. The associate solution model is used to describe the short-range ordering behavior in the liquid phase. The calculations from the present thermodynamic model show good agreement with thermochemical and phase equilibrium data from both the present work and the literature.

36 MATERIALS SCIENCE↗

First-principles study of Al/Al 3 Ni interfaces

Al-Ni alloys have shown promise for high-temperature applications due to the strengthening of Al 3 Ni fibers resistant to coarsening and spheroidization up to 400°C. While the interface between Al and Al 3 Ni phases affects the coarsening rate of Al 3 Ni at elevated temperatures, its characteristics are largely unknown to date. Here, we have constructed various supercells to model this interface and performed a first-principles study based on density functional theory (DFT). We have considered three groups of Al/Al 3 Ni interfaces: experimentally reported orientation relationships from the solidification studies, crystallographically similar Fe-Fe 3 C pearlite interfaces, and the family of low-index (100) termination planes. We have analyzed the correlation between the DFT Al/Al 3 Ni interfacial energies and characteristic features, e.g., excess free volume and the number of broken bonds. We outline the further experimental and computational analysis required to improve the interface modeling of Al/Al 3 Ni.

36 MATERIALS SCIENCE↗

Mechanistic understanding of pH effects on the oxygen evolution reaction

The oxygen-evolution reaction (OER) is pivotal in many energy-conversion technologies as it is an important counter reaction to others that convert stable chemicals to higher-value products using electrochemistry. The local microenvironment and pH for the anode OER can vary from acidic to neutral to alkaline depending on the system being explored, making definitive mechanistic insights difficult. In this paper, we couple experiments, first-principles calculations based on density functional theory, microkinetics, and transport modeling to explore the entire pH range of the OER. At low current densities, neutral pH values unexpectedly perform better than the acidic and alkaline conditions, and this trend is reversed at higher current densities (> 20 mA cm -2 ). Using multiscale modeling, this switch is rationalized by a change from a dual-reaction mechanism to a single rate-determining step. The model also shows how the alkaline reaction rates dominate in the middle to high pH range. Furthermore, we explore that the local pH for near-neutral conditions is much different (e.g., 2.4 at the reaction surface vs. 9 in the bulk) than the pH extremes, demonstrating the criticality that transport phenomena plays in kinetic activity.

36 MATERIALS SCIENCE↗