Iron is a major component of the cores of the Earth and inhabited exoplanets. Its phase diagram at extreme pressures (P) and temperatures (T) is the subject of extensive debate. While recent experiments provide evidence for the stability of the body-centered cubic (bcc) phase, several theoretical studies point to the stability (even though marginal) of the hexagonal close-packed phase (hcp). None of those studies considered the itinerant magnetism of iron at extreme conditions. We compute the high-pressure phase diagram of Fe using density functional theory-based molecular dynamics (DFT MD) in which the paramagnetic nature of Fe is treated within the model of thermally induced longitudinal spin fluctuations (LSF). The LSF DFT MD with 16 valence electrons favors bcc phase stability. Two-phase large-scale simulations with quantum accurate machine learning potentials provide us with both melting and hcp-bcc phase boundaries. The computed phase diagram agrees with most of the experimental data and solves most of the numerous controversies. We conclude that the account for magnetism results in the new physics of iron under extreme conditions and brings the theory in agreement with experiment and seismic data. We expect that the approach we use can be applied to other metals where itinerant magnetism is important.

In this work, we investigate the dislocation-impurity interaction energies and their profiles for various 3d elements —V, Cr, Mn, Cu, Ni, and Co —in and around 1/2〈111〉 screw dislocations in α-Fe using ab initio methods. We consider the ferromagnetic and paramagnetic states, with the latter being modeled through both the disordered local moment model and a spin-wave approach. Our findings reveal that (1) magnetic effects are large compared to size misfit effects of substitutional impurities, and (2) dislocation-impurity interactions are dependent on the magnetic state of the matrix and thermal lattice expansion. In particular, Cu changes from core-attractive in the ferromagnetic state to repulsive in the paramagnetic state.

While first-principles methods have been successfully applied to characterize individual properties of multi-principal element alloys (MPEA), their use in searching for optimal trade-offs between competing properties is hampered by high computational demands. In this work, we present a framework to explore Pareto-optimal compositions by integrating advanced ab initio-based techniques into a Bayesian multi-objective optimization workflow, complemented by a simple analytical model providing straightforward analysis of trends. We benchmark the framework by applying it to solid solution strengthening and ductility of refractory MPEAs, with the parameters of the strengthening and ductility models being efficiently computed using a combination of the coherent-potential approximation method, accounting for finite-temperature effects, and actively-learned moment-tensor potentials parameterized with ab initio data. Properties obtained from ab initio calculations are subsequently used to extend predictions of all relevant material properties to a large class of refractory alloys with the help of the analytical model validated by the data and relying on a few element-specific parameters and universal functions that describe bonding between elements. Our findings offer crucial insights into the traditional strength-vs-ductility dilemma of refractory MPEAs. The proposed framework is versatile and can be extended to other materials and properties of interest, enabling a predictive and tractable high-throughput screening of Pareto-optimal MPEAs over the entire composition space.

To gain a deeper insight into the anomalous yield behavior of Ni₃Al, it is essential to obtain temperature-dependent formation Gibbs energies of the relevant planar defects. Here, the Gibbs energy of the complex stacking fault (CSF) is evaluated using a recently proposed ab initio framework [Acta Materialia, 255 (2023) 118986], accounting for all thermal contributions—including anharmonicity and paramagnetism—up to the melting point. The CSF energy shows a moderate decrease from 300 K to about 1200 K, followed by a stronger drop. We demonstrate the necessity to carefully consider the individual thermal excitations. We also propose a way to analyze the origin of the significant anharmonic contribution to the CSF energy through atomic pair distributions at the CSF plane. With the newly available high-temperature CSF data, an increasing contribution to the energy barrier for the cross-slip process in Ni₃Al with increasing temperature is unveiled, necessitating the refinement of existing analytical models.

Magnetic and atomic ordering in equiatomic FeNi alloy is studied by different ab initio techniques and methods based on density functional theory in order to clarify the main driving forces and their interplay behind these transitions and possibility of their accurate description within standard density functional theory calculations. The Curie temperature is obtained in Monte Carlo simulations using magnetic exchange interactions obtained by applying the magnetic force theorem within multiple scattering theory for different magnetic and atomic configurational states, including account for the thermal atomic displacements and exchange-correlation potential. The calculations show a very strong sensitivity of the results upon exchange-correlation potential, atomic order, and thermal atomic displacements. The calculated Curie temperature of a completely random alloy with the account of thermal lattice displacement is at least about 200 K below the known experimental data (780-800 K) depending on the above mentioned factors. The atomic order-disorder transition temperature is determined from effective chemical interactions, which apart from the chemical contribution (on the ideal fcc lattice) include contributions from lattice thermal vibrations and local lattice relaxations. The effective chemical interactions are strongly affected by the magnetic state, so the order-disorder transition temperature changes between 1000 and 140 K in the fully ordered ferromagnetic and paramagnetic states, respectively. For the reduced magnetization 0.7 (close to the experimental order-disorder transition temperature at 600 K), the order-disorder transition temperature varies between 550 and 700 K depending mostly on the exchange-correlation potential. The latter effect is the uncertainty in the choice of the exchange-correlation approximation in density functional theory calculations.

Antiphase boundaries (APBs) are crucial to understand the anomalous temperature dependence of the yield stress of Ni3Al. However, the required, accurate prediction of temperature-dependent APB energies has been missing. In particular, the impact of magnetism at elevated temperatures has been mostly neglected, based on the argument that Ni3Al is a weak ferromagnet. Here, we show that this is an inappropriate assumption and that - in addition to anharmonic and electronic excitations - thermally-induced magnetic spin fluctuations strongly affect the APB energies, especially for the (100)APB with an increase of nearly up to 40% over the nonmagnetic data. We utilize an ab initio framework that incorporates explicit lattice vibrations, electronic excitations, and the impact of magnetic excitations up to the melting temperature. Our results prompt to take full account of thermally-induced spin fluctuations even for weak itinerant ferromagnetic materials. Consequences for large-scale modeling in Ni-based superalloys, e.g., of dislocations or the elastic-plastic behavior, can be expected.

High-temperature properties of ceria surfaces are important for many applications. Here, we report the temperature dependencies of surface energy for (111) and (110) CeO2 obtained in the framework of the extended two-stage up-sampled thermodynamic integration using Langevin dynamics. The method was used together with machine-learning potentials called moment tensor potentials (MTPs), which were fitted to the results of the ab initio molecular dynamics calculations for (111) and (110) CeO2 at different temperatures. The parameters of MTP training and fitting were tested, and the optimal algorithm for the ceria systems was proposed. We found that the temperature increases from 0 to 2100 K led to the decrease of the Helmholtz free energy of (111) CeO2 from 0.78 to 0.64 J/m2. The energy of (110) CeO2 dropped from 1.19 J/m2 at 0 K to 0.92 J/m2 at 1800 K. We show that it is important to consider anharmonicity, as simple consideration of volume expansion gives the wrong temperature dependencies of the surface energies.

It is demonstrated that thermally induced longitudinal spin fluctuations (LSF) play an important role in itinerant Co3Mn2Ge at an elevated temperature. The effect of LSF is taken into account during ab initio calculations via a simple model for the corresponding entropy contribution. We show that the magnetic entropy leads to the appearance of a medium size local moment on Co atoms. As a consequence, this leads to a renormalization of the magnetic exchange interactions with a quite substantial impact upon the calculated Curie temperature. Taking LSF into account, the calculated Curie temperature can be brought to be in good agreement with the experimental value.

Heusler compounds represent a unique class of materials that exhibit a wide range of fascinating and tuneable properties such as exotic magnetic phases, superconductivity, band topology, or thermoelectricity. An exceptional, but for Heusler compounds common, feature is that they are prone to antisite defects and disorder. In this regard, the Fe2VAl Heusler compound has been a particularly interesting and disputed candidate. Even though various theoretical scenarios for the interplay of physical properties and disorder have been proposed, the metastable disordered A2 phase hitherto precluded experimental investigation in bulk samples. Here, we report experimental results on disorder-tuned Fe2VAl0.9Si0.1 alloys all the way toward the A2 phase, which we realized via rapidly quenching our samples from high temperatures. We measured the thermoelectric properties of these materials in a wide temperature range (4 to 700 K); they suggest a gradual semimetal/narrow-gap semiconductor -> metal transition upon increasing the disorder. We also find a large anomalous Hall effect in the disordered A2 phase, arising from the side-jump scattering of charge carriers at the antisite magnetic moments. This is corroborated by measurements of the temperature-and field-dependent magnetization, which increases dramatically up to approximate to 2.5 mu B/f.u. as compared to the ordered compound (<0.1 mu B/f.u.). This study provides an experimental realization of the metastable A2 structure in bulk Fe2VAl-based alloys and grants insight into the structure-property relationship of these materials. Our work confirms that temperature-induced antisite disorder, occurring during thermal heat treatment, can be a precisely tuneable parameter in the family of Heusler compounds.

The surface free energies of seven different facets of tungsten (W) are obtained up to the melting point with full account of all the relevant thermal excitations; in particular, thermal atomic vibrations, electronic excitations, and their mutual coupling. The latter is done using ab initio molecular dynamics simulations coupled with the thermodynamic integration technique. In this way, the calculations contain almost no error but the one related to the used exchange-correlation functional, which makes the results truly first principles. The obtained results are compared with previous quasiharmonic calculations for the surface free energies of W and experimental data. The anharmonic contribution is, as expected, important for open surfaces at high temperatures, which leads to a temperature dependence of the surface energy anisotropy. The calculated Wulff shapes and surface energies are in excellent agreement with experimental data close to the melting point, where the crystalline structure of the surface layers is destroyed by a dramatic mobility of the atoms there.