Caloric effects around phase transitions in magnetic materials described by ab initio theory : the electronic glue and fluctuating local moments

We describe magneto-, baro-, and elastocaloric effects (MCEs, BCEs, and eCEs) in materials, which possess both discontinuous (first-order) and continuous (second-order) magnetic phase transitions. Our ab initio theory of the interacting electrons of materials in terms of disordered local moments has produced explicit mechanisms for the drivers of these transitions, and here, we study associated caloric effects in three case studies where both types of transition are evident. Our earlier work had described FeRh’s magnetic phase diagram and large MCE. Here, we present calculations of its substantial BCE and eCE. We describe the MCE of dysprosium and find very good agreement with experimental values for isothermal entropy ((ΔSiso) and adiabatic temperature (ΔTad) changes over a large temperature span and different applied magnetic field values. We examine the conditions for optimal values of both ΔSiso and ΔTad that comply with a Clausius–Clapeyron analysis, which we use to propose a promising elastocaloric cooling cycle arising from the unusual dependence of the entropy on temperature and biaxial strain found in our third case study—the Mn3GaN antiperovskite. We explain how both ΔSiso and ΔTad can be kept large by exploiting the complex tensile strain–temperature magnetic phase diagram, which we had earlier predicted for this material and also propose that hysteresis effects will be absent from half of the caloric cycle. This rich and complex behavior stems from the frustrated nature of the interactions among the Mn local moments

Improvement of magnetic hardness at finite temperatures: ab initio disordered local moment approach for YCo5_5

Temperature dependence of the magnetocrystalline anisotropy energy and magnetization of the prototypical rare-earth magnet YCo$_5$ is calculated from first principles, utilizing the relativistic disordered local moment approach. We discuss a strategy to enhance the finite-temperature anisotropy field by hole doping, paving the way for an improvement of the coercivity near room temperature or higher.Comment: 12 pages, 13 figures, some corrections made and a reference update

First-order ferromagnetic transitions of lanthanide local moments in divalent compounds: An itinerant electron positive feedback mechanism and Fermi surface topological change

Around discontinuous (first-order) magnetic phase transitions the strong caloric response of materials to the application of small fields is widely studied for the development of solid-state refrigeration. Typically strong magnetostructural coupling drives such transitions and the attendant substantial hysteresis dramatically reduces the cooling performance. In this context we describe a purely electronic mechanism which pilots a first-order paramagnetic-ferromagnetic transition in divalent lanthanide compounds and which explains the giant non-hysteretic magnetocaloric effect recently discovered in a Eu$_2$In compound. There is positive feedback between the magnetism of itinerant valence electrons and the ferromagnetic ordering of local $f$-electron moments, which appears as a topological change to the Fermi surface. The origin of this electronic mechanism stems directly from Eu's divalency, which explains the absence of a similar discontinuous transition in Gd$_2$In.Comment: 8 pages, 7 figure

Temperature-dependent magnetocrystalline anisotropy of rare earth/transition metal permanent magnets from first principles : the light RCo5 (R = Y, La-Gd) intermetallics

Computational design of more efficient rare earth/transition metal (RE-TM) permanent magnets requires accurately calculating the magnetocrystalline anisotropy (MCA) at finite temperature, since this property places an upper bound on the coercivity. Here, we present a first-principles methodology to calculate the MCA of RE-TM magnets which fully accounts for the effects of temperature on the underlying electrons. The itinerant electron TM magnetism is described within the disordered local moment picture, and the localized RE-4f magnetism is described within crystal field theory. We use our model, which is free of adjustable parameters, to calculate the MCA of the RCo5 (R=Y, La-Gd) magnet family for temperatures 0–600 K. We correctly find a huge uniaxial anisotropy for SmCo5 (21.3MJm−3 at 300 K) and two finite temperature spin reorientation transitions for NdCo5. The calculations also demonstrate dramatic valency effects in CeCo5 and PrCo5. Our calculations provide quantitative, first-principles insight into several decades of RE-TM experimental studies

Rare-earth transition-metal magnets at finite temperature : self-interaction-corrected relativistic density functional theory in the disordered local-moment picture

Atomic-scale computational modeling of technologically-relevant permanent magnetic materials faces two key challenges. First, a material's magnetic properties depend sensitively on temperature, so the calculations must account for thermally-induced magnetic disorder. Second, the most widely-used permanent magnets are based on rare-earth elements, whose highly-localized 4f electrons are poorly described by standard electronic structure methods. Here, we take two established theories --- the disordered local moment picture of thermally-induced magnetic disorder and self-interaction-corrected density-functional theory --- and devise a computational framework to overcome these challenges. Using the new approach, we calculate magnetic moments and Curie temperatures of the rare-earth cobalt (RECo5) family for RE=Y--Lu. The calculations correctly reproduce the experimentally-measured trends across the series and confirm that, apart from the hypothetical compound EuCo5, SmCo5 has the strongest magnetic properties at high temperature. An order parameter analysis demonstrates that varying the RE has a surprisingly strong effect on the Co--Co magnetic interactions determining the Curie temperature, even when the lattice parameters are kept fixed. We propose the origin of this behavior is a small contribution to the density from f-character electrons located close to the Fermi level

Theory of magnetic ordering in the heavy rare earths : ab initio electronic origin of pair- and four-spin interactions

We describe a disordered local moment theory for long-period magnetic phases and investigate the temperature and magnetic field dependence of the magnetic states in the heavy rare earth elements (HREs), namely, paramagnetic, conical and helical antiferromagnetic (HAFM), fan, and ferromagnetic (FM) states. We obtain a generic HRE magnetic phase diagram which is consequent on the response of the common HRE valence electronic structure to f-electron magnetic moment ordering. The theory directly links the first-order HAFM-FM transition to the loss of Fermi surface nesting, induced by this magnetic ordering, as well as provides a template for analyzing the other phases and exposing where f-electron correlation effects are particularly intricate. Gadolinium, for a range of hexagonal, close-packed lattice constants c and a, is the prototype, described ab initio, and applications to other HREs are made straightforwardly by scaling the effective pair and quartic local moment interactions that emerge naturally from the theory with de Gennes factors and choosing appropriate lanthanide-contracted c and a values

Crystal field coefficients for yttrium analogues of rare-earth/transition-metal magnets using density-functional theory in the projector-augmented wave formalism

We present a method of calculating crystal field coefficients of rare-earth/transition-metal (RE-TM) magnets within density-functional theory (DFT). The principal idea of the method is to calculate the crystal field potential of the yttrium analogue ("Y-analogue") of the RE-TM magnet, i.e. the material where the lanthanide elements have been substituted with yttrium. The advantage of dealing with Y-analogues is that the methodological and conceptual difficulties associated with treating the highly-localized 4<i>f</i> electrons in DFT are avoided, whilst the nominal valence electronic structure principally responsible for the crystal field is preserved. In order to correctly describe the crystal field potential in the core region of the atoms we use the projector-augmented wave formalism of DFT, which allows the reconstruction of the full charge density and electrostatic potential. The Y-analogue crystal field potentials are combined with radial 4<i>f</i> charge densities obtained in self-interaction-corrected calculations on the lanthanides to obtain crystal field coefficients. We demonstrate our method on a test set of 10 materials comprising 9 RE-TM magnets and elemental Tb. We show that the calculated easy directions of magnetization agree with experimental observations, including a correct description of the anisotropy within the basal plane of Tb and NdCo<sub>5</sub>. We further show that the Y-analogue calculations generally agree quantitatively with previous calculations using the open-core approximation to treat the 4<i>f</i> electrons, and argue that our simple approach may be useful for large-scale computational screening of new magnetic materials

Effects of short-range order on the electronic structure of disordered metallic systems

For many years the Korringa-Kohn-Rostoker coherent-potential approximation (KKR-CPA) has been widely used to describe the electronic structure of disordered systems based upon a first-principles description of the crystal potential. However, as a single-site theory the KKR-CPA is unable to account for important environmental effects such as short-range order (SRO) in alloys and spin fluctuations in magnets, amongst others. Using the recently devised KKR-NLCPA (where NL stands for nonlocal), we show how to remedy this by presenting explicit calculations for the effects of SRO on the electronic structure of the bcc Cu_{50}Zn_{50} solid solution.Comment: 8 pages, 6 figures, Revised versio

First-principles calculations of the magnetocrystalline anisotropy of the prototype 2:17 cell boundary phase YCo1-x-yFexCuy5

We present a computational study of the compound for 0 . This compound was chosen as a prototype for investigating the cell boundary phase believed to play a key role in establishing the high coercivity of commercial Sm-Co 2:17 magnets. Using density-functional theory, we have calculated the magnetization and magnetocrystalline anisotropy at zero temperature for a range of compositions, modeling the doped compounds within the coherent potential approximation. We have also performed finite temperature calculations for , and within the disordered local moment picture. Our calculations find that substituting Co with small amounts of either Fe or Cu boosts the magnetocrystalline anisotropy K, but the change in K depends strongly on the location of the dopants. Furthermore, the calculations do not show a particularly large difference between the magnetic properties of Cu-rich and equal Fe-Cu , despite these two compositions showing different coercivity behavior when found in the cell boundary phase of 2:17 magnets. Our study lays the groundwork for studying the rare earth contribution to the anisotropy of, and also shows how a small amount of transition metal substitution can boost the anisotropy field of

Tuning the metamagnetism of an antiferromagnetic metal

We describe a `disordered local moment' (DLM) first-principles electronic structure theory which demonstrates that tricritical metamagnetism can arise in an antiferromagnetic metal due to the dependence of local moment interactions on the magnetisation state. Itinerant electrons can therefore play a defining role in metamagnetism in the absence of large magnetic anisotropy. Our model is used to accurately predict the temperature dependence of the metamagnetic critical fields in CoMnSi-based alloys, explaining the sensitivity of metamagnetism to Mn-Mn separations and compositional variations found previously. We thus provide a finite-temperature framework for modelling and predicting new metamagnets of interest in applications such as magnetic cooling