Calculation of solubility in titanium alloys from first-principles

We present an approach to calculate the atomic bulk solubility in binary alloys based on the statistical-thermodynamic theory of dilute lattice gas. The model considers all the appropriate ground states of the alloy and results in a simple Arrhenius-type temperature dependence determined by a {\it "low-solubility formation enthalpy"}. This quantity, directly obtainable from first-principle calculations, is defined as the composition derivative of the compound formation enthalpy with respect to nearby ground states. We apply the framework and calculate the solubility of the A specie in A-Ti alloys (A=Ag,Au,Cd,Co,Cr,Ir,W,Zn). In addition to determining unknown low-temperature ground states for the eight alloys, we find qualitative agreements with solubility experimental results. The presented formalism, correct in the low-solubility limit, should be considered as an appropriate starting point for determining if more computationally expensive formalisms are otherwise needed.Comment: 10 pages, 12 figure

Study of phase stability of MnCr using the augmented space recursion based orbital peeling technique

In an earlier communication we have developed a recursion based approach to the study of phase stability and transition of binary alloys. We had combined the recursion method introduced by Haydock, Heine and Kelly and the our augmented space approach with the orbital peeling technique proposed by Burke to determine the small energy differences involved in the discussion of phase stability. We extend that methodology for the study of MnCr alloys.Comment: 11 page

First-principles study of the Fe

MgO bilayer systems emphasizing the influence of the iron layer thickness on the geometry, the electronic structure and the magnetic properties. Our calculations ensure the unconstrained structural relaxation at scalar relativistic level for various numbers of iron layers placed on the magnesium oxide substrate. Our results show that due to the formation of the interface the electronic structure of the interface iron atoms is significantly modified involving charge transfer within the iron subsystem. In addition, we find that the magnetic anisotropy energy increases from 1.9 mJ m-2 for 3 Fe layers up to 3.0 mJ m-2 for 11 Fe layers

Site-resolved contributions to the magnetic anisotropy energy and complex spin structure of Fe/MgO sandwiches

Fe/MgO-based Magnetic Tunnel Junctions (MTJs) are among the most promising candidates for spintronic devices due to their high thermal stability and high tunneling magnetoresistance. Despite its apparent simplicity, the nature of the interactions between the Fe and MgO layers leads to complex finite size effects and temperature dependent magnetic properties which must be carefully controlled for practical applications. In this letter, we investigate the electronic, structural and magnetic properties of MgO/Fe/MgO sandwiches using first principles calculations and atomistic spin modeling based on a fully parameterized spin Hamiltonian. We find a large contribution to the effective interfacial magnetic anisotropy from the two-ion exchange energy. Minimization of the total energy using atomistic simulations shows a surprising spin spiral ground state structure at the interface owing to frustrated ferromagnetic and antiferromagnetic interactions, leading to a reduced Curie temperature and strong layer-wise temperature dependence of the magnetization. The different temperature dependences of the interface and bulk-like layers results in an unexpected non-monotonic temperature variation of the effective magnetic anisotropy energy and temperature-induced spin-reorientation transition to an in-plane magnetization at low temperatures. Our results demonstrate the intrinsic physical complexity of the pure Fe/MgO interface and the role of elevated temperatures providing new insight when interpreting experimental data of nanoscale MTJs

Ordered phases in ruthenium binary alloys from high-throughput first-principles calculations

Despite the increasing importance of ruthenium in numerous technological applications, e.g., catalysis and electronic devices, experimental and computational data on its binary alloys are sparse. In particular, data are scant on those binary systems believed to be phase-separating. We performed a comprehensive study of ruthenium binary systems with the 28 transition metals, using high-throughput first-principles calculations. These computations predict novel unsuspected compounds in 7 of the 16 binary systems previously believed to be phase-separating and in two of the three systems reported with only a high-temperature σ phase. They also predict a few unreported compounds in five additional systems and indicate that some reported compounds may actually be unstable at low temperature. These new compounds may be useful in the rational design of new Ru-based catalysts. The following systems are investigated: AgRu, AuRu, CdRu, CoRu, CrRu, CuRu, FeRu, HfRu, HgRu, IrRu, MnRu, MoRu, NbRu, NiRu, OsRu, PdRu, PtRu, ReRu, RhRu, RuSc, RuTa, RuTc, RuTi, RuV, RuW, RuY, RuZn, and RuZr (a star denotes systems in which the ab initio method predicts that no compounds are stable)

First-principle solubilities of alkali and alkaline earth metals in Mg-B alloys

By devising a novel framework, we present a comprehensive theoretical study of solubilities of alkali (Li, Na, K, Rb, Cs) and alkaline earth (Be, Ca, Sr, Ba) metals in the he boron-rich Mg-B system. The study is based on first-principle calculations of solutes formation energies in MgB$_2$, MgB$_4$, MgB$_7$ alloys and subsequent statistical-thermodynamical evaluation of solubilities. The advantage of the approach consists in considering all the known phase boundaries in the ternary phase diagram. Substitutional Na, Ca, and Li demonstrate the largest solubilities, and Na has the highest (0.5-1 % in MgB$_7$ at $T=650-1000$ K). All the considered interstitials have negligible solubilities. The solubility of Be in MgB$_7$ can not be determined because the corresponding low-solubility formation energy is negative indicating the existence of an unknown ternary ground state. We have performed a high-throughput search of ground states in binary Mg-B, Mg-$A$, and B-$A$ systems, and we construct the ternary phase diagrams of Mg-B-$A$ alloys based on the stable binary phases. Despite its high temperature observations, we find that Sr$_{9}$Mg$_{38}$ is not a low-temperature equilibrium structure. We also determine two new possible ground states CaB$_{4}$ and RbB$_{4}$, not yet observed experimentally.Comment: 5 figure

Configurational Thermodynamics of Alloyed Nanoparticles with Adsorbates

Changes in the chemical configuration of alloyed nanoparticle (NP) catalysts induced by adsorbates under working conditions, such as reversal in core–shell preference, are crucial to understand and design NP functionality. We extend the cluster expansion method to predict the configurational thermodynamics of alloyed NPs with adsorbates based on density functional theory data. Exemplified with PdRh NPs having O-coverage up to a monolayer, we fully detail the core–shell behavior across the entire range of NP composition and O-coverage with quantitative agreement to in situ experimental data. Optimally fitted cluster interactions in the heterogeneous system are the key to enable quantitative Monte Carlo simulations and design