Accelerated materials design approaches based on structural classification: Application to low enthalpy high pressure phases of SH₃ and SeH₃

We propose a methodology that efficiently ass-eses major characteristics in the energy landscape for agiven space of configurations (crystal structures) underpressure. In this work we study SH3 and SeH3, both of fun-damental interest due to their superconducting properties.Starting from the crystal fingerprint, which defines config-urational distances between crystalline structures, we in-troduce an optimal one dimensional metric space that isused to both classify and characterize the structures. Fur-thermore, this is correlated to the electronic structure. Ouranalysis highlights the uniqueness of the Im-3m phase of H3S and H33Se for superconductivity. This approach isan useful tool for future material design applications

Emergence of superconductivity in doped H₂O ice at high pressure

We investigate the possibility of achieving high-temperature superconductivity in hydrides under pressure by inducing metallization of otherwise insulating phases through doping, a path previously used to render standard semiconductors superconducting at ambient pressure. Following this idea, we study H2O, one of the most abundant and well-studied substances, we identify nitrogen as the most likely and promising substitution/dopant. We show that for realistic levels of doping of a few percent, the phase X of ice becomes superconducting with a critical temperature of about 60 K at 150 GPa. In view of the vast number of hydrides that are strongly covalent bonded, but that remain insulating up to rather large pressures, our results open a series of new possibilities in the quest for novel high-temperature superconductors

Emergence of hidden phases of methylammonium lead iodide (CH3NH3PbI3) upon compression

We perform a thorough structural search with the minima hopping method (MHM) to explore low-energy structures of methylammonium lead iodide. By combining the MHM with a forcefield, we efficiently screen vast portions of the configurational space with large simulation cells containing up to 96 atoms. Our search reveals two structures of methylammonium iodide perovskite (MAPI) that are substantially lower in energy than the well-studied experimentally observed low-temperature Pnma orthorhombic phase according to density functional calculations. Both structures have not yet been reported in the literature for MAPI, but our results show that they could emerge as thermodynamically stable phases via compression at low temperatures. In terms of the electronic properties, the two phases exhibit larger band gaps than the standard perovskite-type structures. Hence, the pressure-induced phase selection at technologically achievable pressures (i.e., via thin-film strain) is a viable route towards the synthesis of several MAPI polymorph with variable band gaps

The elephant in the room of density functional theory calculations

Using multiwavelets, we have obtained total energies and corresponding atomization energies for the GGA-PBE and hybrid-PBE0 density functionals for a test set of 211 molecules with an unprecedented and guaranteed μHartree accuracy. These quasi-exact references allow us to quantify the accuracy of standard all-electron basis sets that are believed to be highly accurate for molecules, such as Gaussian-type orbitals (GTOs), all-electron numeric atom-centered orbitals (NAOs), and full-potential augmented plane wave (APW) methods. We show that NAOs are able to achieve the so-called chemical accuracy (1 kcal/mol) for the typical basis set sizes used in applications, for both total and atomization energies. For GTOs, a triple-ζquality basis has mean errors of ∼10 kcal/mol in total energies, while chemical accuracy is almost reached for a quintuple-ζbasis. Due to systematic error cancellations, atomization energy errors are reduced by almost an order of magnitude, placing chemical accuracy within reach also for medium to large GTO bases, albeit with significant outliers. In order to check the accuracy of the computed densities, we have also investigated the dipole moments, where in general only the largest NAO and GTO bases are able to yield errors below 0.01 D. The observed errors are similar across the different functionals considered here

High-pressure synthesis of Ba2RhO4, a rhodate analog of the layered perovskite Sr-ruthenate

A layered perovskite-type oxide Ba2RhO4 was synthesized by a high-pressure technique with the support of convex-hull calculations. The crystal and electronic structure were studied by both experimental and computational tools. Structural refinements for powder x-ray diffraction data showed that Ba2RhO4 crystallizes in a K2NiF4-type structure, isostructural to Sr2RuO4 and Ba2IrO4. Magnetic, resistivity, and specific-heat measurements for polycrystalline samples of Ba2RhO4 indicate that the system can be characterized as a correlated metal. Despite the close similarity to its Sr2RuO4 counterpart in the electronic specific-heat coefficient and the Wilson ratio, Ba2RhO4 shows no signature of superconductivity down to 0.16 K. Whereas the Fermi surface topology has reminiscent pieces of Sr2RuO4, an electronlike eg-(dx2-y2) band descends below the Fermi level, making this compound unique also as a metallic counterpart of the spin-orbit coupled Mott insulator Ba2IrO4

Pressure-Tuneable Visible-Range Band Gap in the Ionic Spinel Tin Nitride

The application of pressure allows systematic tuning of the charge density of a material cleanly, that is, without changes to the chemical composition via dopants, and exploratory high-pressure experiments can inform the design of bulk syntheses of materials that benefit from their properties under compression. The electronic and structural response of semiconducting tin nitride Sn3N4 under compression is now reported. A continuous opening of the optical band gap was observed from 1.3 eV to 3.0 eV over a range of 100 GPa, a 540 nm blue-shift spanning the entire visible spectrum. The pressure-mediated band gap opening is general to this material across numerous high-density polymorphs, implicating the predominant ionic bonding in the material as the cause. The rate of decompression to ambient conditions permits access to recoverable metastable states with varying band gaps energies, opening the possibility of pressure-tuneable electronic properties for future applications

Understanding Novel Superconductors with Ab Initio Calculations

This chapter gives an overview of the progress in the field of computational superconductivity. Following the MgB2 discovery (2001), there has been an impressive acceleration in the development of methods based on Density Functional Theory to compute the critical temperature and other physical properties of actual superconductors from first-principles. State-of-the-art ab-initio methods have reached predictive accuracy for conventional (phonon-mediated) superconductors, and substantial progress is being made also for unconventional superconductors. The aim of this chapter is to give an overview of the existing computational methods for superconductivity, and present selected examples of material discoveries that exemplify the main advancements.Comment: 38 pages, 10 figures, Contribution to Springer Handbook of Materials Modellin

Crystal structure prediction of magnetic materials

We present a methodology to predict magnetic systems using ab initio methods. By employing crystal structure method and spin-polarized calculations, we explore the relation between crystalline structures and their magnetic properties. In this work, testbed cases of transition metal alloys (FeCr, FeMn, FeCo and FeNi) are study in the ferromagnetic case. Wefind soft-magnetic properties for FeCr, FeMn while for FeCo and FeNi hard-magnetic are predicted. In particular, for the family of FeNi, a candidate structure with energy lower than the tetrataenite was found. The structure has a saturation magnetization (Ms) of 1.2 MA m-1, magnetic anisotropy energy (MAE) above 1200 kJm-3 and hardness value close to 1. Theoretically, this system made of abundant elements could be the right candidate for permanent magnet applications. Comparing with the state-of-the-art (Nd2Fe14B) hard-magnet, (Ms of 1.28 MA m-1 and MAE of 4900 kJm-3) is appealing to explore this low energy polymorph of FeNi further. Considering the relatively limited number of magnets, predicting a new system may open routes for free rare-earth magnets. Furthermore, the use of the computational algorithm as the one presented in this work, hold promises in thisfield for which in near future improvements will allow to study numerous complex systems, larger simulations cells and tackled long-range antiferromagnetic cases

High temperature superconductivity in sulfur and selenium hydrides at high pressure

Due to its low atomic mass, hydrogen is the most promising element to search for hightemperature phononic superconductors. However, metallic phases of hydrogen are only expected at extreme pressures (400 GPa or higher). The measurement of the record superconducting critical temperature of 203 K in a hydrogen-sulfur compound at 160 GPa of pressure [A.P. Drozdov, M.I. Eremets, I.A. Troyan, arXiv:1412.0460 [cond-mat.supr-con] (2014); A.P. Drozdov, M.I. Eremets, I.A. Troyan, V. Ksenofontov, S.I. Shylin, Nature 525, 73 (2015)], shows that metallization of hydrogen can be reached at significantly lower pressure by inserting it in the matrix of other elements. In this work we investigate the phase diagram and the superconducting properties of the H-S systems by means of minima hopping method for structure prediction and density functional theory for superconductors. We also show that Se-H has a similar phase diagram as its sulfur counterpart as well as high superconducting critical temperature. We predict H3Se to exceed 120 K superconductivity at 100 GPa. We show that both H3Se and H3S, due to the critical temperature and peculiar electronic structure, present rather unusual superconducting properties