Ab initio study on the effects of transition metal doping of Mg2NiH4

Mg2NiH4 is a promising hydrogen storage material with fast (de)hydrogenation kinetics. Its hydrogen desorption enthalpy, however, is too large for practical applications. In this paper we study the effects of transition metal doping by first-principles density functional theory calculations. We show that the hydrogen desorption enthalpy can be reduced by ~0.1 eV/H2 if one in eight Ni atoms is replaced by Cu or Fe. Replacing Ni by Co atoms, however, increases the hydrogen desorption enthalpy. We study the thermodynamic stability of the dopants in the hydrogenated and dehydrogenated phases. Doping with Co or Cu leads to marginally stable compounds, whereas doping with Fe leads to an unstable compound. The optical response of Mg2NiH4 is also substantially affected by doping. The optical gap in Mg2NiH4 is ~1.7 eV. Doping with Co, Fe or Cu leads to impurity bands that reduce the optical gap by up to 0.5 eV.Comment: 8 pages, 4 figure

Automation methodologies and large-scale validation for GWGW, towards high-throughput GWGW calculations

The search for new materials, based on computational screening, relies on methods that accurately predict, in an automatic manner, total energy, atomic-scale geometries, and other fundamental characteristics of materials. Many technologically important material properties directly stem from the electronic structure of a material, but the usual workhorse for total energies, namely density-functional theory, is plagued by fundamental shortcomings and errors from approximate exchange-correlation functionals in its prediction of the electronic structure. At variance, the $GW$ method is currently the state-of-the-art {\em ab initio} approach for accurate electronic structure. It is mostly used to perturbatively correct density-functional theory results, but is however computationally demanding and also requires expert knowledge to give accurate results. Accordingly, it is not presently used in high-throughput screening: fully automatized algorithms for setting up the calculations and determining convergence are lacking. In this work we develop such a method and, as a first application, use it to validate the accuracy of $G_0W_0$ using the PBE starting point, and the Godby-Needs plasmon pole model ($G_0W_0^\textrm{GN}$@PBE), on a set of about 80 solids. The results of the automatic convergence study utilized provides valuable insights. Indeed, we find correlations between computational parameters that can be used to further improve the automatization of $GW$ calculations. Moreover, we find that $G_0W_0^\textrm{GN}$@PBE shows a correlation between the PBE and the $G_0W_0^\textrm{GN}$@PBE gaps that is much stronger than that between $GW$ and experimental gaps. However, the $G_0W_0^\textrm{GN}$@PBE gaps still describe the experimental gaps more accurately than a linear model based on the PBE gaps.Comment: 12 pages, 11 figure

The PseudoDojo: Training and grading a 85 element optimized norm-conserving pseudopotential table

First-principles calculations in crystalline structures are often performed with a planewave basis set. To make the number of basis functions tractable two approximations are usually introduced: core electrons are frozen and the diverging Coulomb potential near the nucleus is replaced by a smoother expression. The norm-conserving pseudopotential was the first successful method to apply these approximations in a fully ab initio way. Later on, more efficient and more exact approaches were developed based on the ultrasoft and the projector augmented wave formalisms. These formalisms are however more complex and developing new features in these frameworks is usually more difficult than in the norm-conserving framework. Most of the existing tables of norm- conserving pseudopotentials, generated long ago, do not include the latest developments, are not systematically tested or are not designed primarily for high accuracy. In this paper, we present our PseudoDojo framework for developing and testing full tables of pseudopotentials, and demonstrate it with a new table generated with the ONCVPSP approach. The PseudoDojo is an open source project, building on the AbiPy package, for developing and systematically testing pseudopotentials. At present it contains 7 different batteries of tests executed with ABINIT, which are performed as a function of the energy cutoff. The results of these tests are then used to provide hints for the energy cutoff for actual production calculations. Our final set contains 141 pseudopotentials split into a standard and a stringent accuracy table. In total around 70.000 calculations were performed to test the pseudopotentials. The process of developing the final table led to new insights into the effects of both the core-valence partitioning and the non-linear core corrections on the stability, convergence, and transferability of norm-conserving pseudopotentials. ...Comment: abstract truncated, 17 pages, 25 figures, 8 table

A model for the formation energies of alanates and boranates

We develop a simple model for the formation energies (FEs) of alkali and lkaline earth alanates and boranates, based upon ionic bonding between metal cations and (AlH4)- or (BH4)- anions. The FEs agree well with values obtained from first principles calculations and with experimental FEs. The model shows that details of the crystal structure are relatively unimportant. The small size of the (BH4)- anion causes a strong bonding in the crystal, which makes boranates more stable than alanates. Smaller alkali or alkaline earth cations do not give an increased FE. They involve a larger ionization potential that compensates for the increased crystal bonding.Comment: 3 pages, 2 figure

First-principles study of the optical properties of MgxTi(1-x)H2

The optical and electronic properties of Mg-Ti hydrides are studied using first-principles density functional theory. Dielectric functions are calculated for MgxTi(1-x)H2 with compositions x = 0.5, 0.75, and 0.875. The structure is that of fluorite TiH2 where both Mg and Ti atoms reside at the Ti positions of the lattice. In order to assess the effect of randomness in the Mg and Ti occupations we consider both highly ordered structures, modeled with simple unit cells of minimal size, and models of random alloys. These are simulated by super cells containing up to 64 formula units (Z = 64). All compositions and structural models turn out metallic, hence the dielectric functions contain interband and intraband free electron contributions. The former are calculated in the independent particle random phase approximation. The latter are modeled based upon the intraband plasma frequencies, which are also calculated from first-principles. Only for the models of the random alloys we obtain a black state, i.e. low reflection and transmission in the energy range from 1 to 6 eV.Comment: 7 pages, 8 figure

Electronic structure and optical properties of lightweight metal hydrides

We study the electronic structures and dielectric functions of the simple hydrides LiH, NaH, MgH2 and AlH3, and the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4 and Mg(AlH4)2, using first principles density functional theory and GW calculations. All these compounds are large gap insulators with GW single particle band gaps varying from 3.5 eV in AlH3 to 6.5 eV in the MAlH4 compounds. The valence bands are dominated by the hydrogen atoms, whereas the conduction bands have mixed contributions from the hydrogens and the metal cations. The electronic structure of the aluminium compounds is determined mainly by aluminium hydride complexes and their mutual interactions. Despite considerable differences between the band structures and the band gaps of the various compounds, their optical responses are qualitatively similar. In most of the spectra the optical absorption rises sharply above 6 eV and has a strong peak around 8 eV. The quantitative differences in the optical spectra are interpreted in terms of the structure and the electronic structure of the compounds.Comment: 13 pages, 10 figure

DFT Study of Planar Boron Sheets: A New Template for Hydrogen Storage

We study the hydrogen storage properties of planar boron sheets and compare them to those of graphene. The binding of molecular hydrogen to the boron sheet (0.05 eV) is stronger than that to graphene. We find that dispersion of alkali metal (AM = Li, Na, and K) atoms onto the boron sheet markedly increases hydrogen binding energies and storage capacities. The unique structure of the boron sheet presents a template for creating a stable lattice of strongly bonded metal atoms with a large nearest neighbor distance. In contrast, AM atoms dispersed on graphene tend to cluster to form a bulk metal. In particular the boron-Li system is found to be a good candidate for hydrogen storage purposes. In the fully loaded case this compound can contain up to 10.7 wt. % molecular hydrogen with an average binding energy of 0.15 eV/H2.Comment: 19 pages, 7 figures, and 3 table

Quasiparticle interfacial level alignment of highly hybridized frontier levels: H2_2O on TiO2_2(110)

Knowledge of the frontier levels' alignment prior to photo-irradiation is necessary to achieve a complete quantitative description of H$_2$O photocatalysis on TiO$_2$(110). Although H$_2$O on rutile TiO$_2$(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H$_2$O occupied levels is still lacking. For experiment, this is due to the H$_2$O levels being obscured by hybridization with TiO$_2$(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H$_2$O-TiO$_2$(110) interface. Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) $G_0W_0$, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H$_2$O on TiO$_2$(110). We perform this separation as a function of H$_2$O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO$_2$(110) surface, the H$_2$O 3a$_1$ and 1b$_1$ levels are broadened into several peaks between 5 and 1 eV below the TiO$_2$(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H$_2$O adsorbed intact and dissociated on stoichiometric TiO$_2$(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H$_2$O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QP$GW$ (scQP$GW$1) to obtain the ionization potential of the H$_2$O-TiO$_2$(110) interface.Comment: 12 pages, 12 figures, 1 tabl

Ionic high-pressure form of elemental boron

Boron is an element of fascinating chemical complexity. Controversies have shrouded this element since its discovery was announced in 1808: the new 'element' turned out to be a compound containing less than 60-70 percent of boron, and it was not until 1909 that 99-percent pure boron was obtained. And although we now know of at least 16 polymorphs, the stable phase of boron is not yet experimentally established even at ambient conditions. Boron's complexities arise from frustration: situated between metals and insulators in the periodic table, boron has only three valence electrons, which would favour metallicity, but they are sufficiently localized that insulating states emerge. However, this subtle balance between metallic and insulating states is easily shifted by pressure, temperature and impurities. Here we report the results of high-pressure experiments and ab initio evolutionary crystal structure predictions that explore the structural stability of boron under pressure and, strikingly, reveal a partially ionic high-pressure boron phase. This new phase is stable between 19 and 89 GPa, can be quenched to ambient conditions, and has a hitherto unknown structure (space group Pnnm, 28 atoms in the unit cell) consisting of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement. We find that the ionicity of the phase affects its electronic bandgap, infrared adsorption and dielectric constants, and that it arises from the different electronic properties of the B2 pairs and B12 clusters and the resultant charge transfer between them.Comment: Published in Nature 453, 863-867 (2009

Epidemiology, patterns of care, and mortality for patients with acute respiratory distress syndrome in intensive care units in 50 countries

IMPORTANCE: Limited information exists about the epidemiology, recognition, management, and outcomes of patients with the acute respiratory distress syndrome (ARDS). OBJECTIVES: To evaluate intensive care unit (ICU) incidence and outcome of ARDS and to assess clinician recognition, ventilation management, and use of adjuncts-for example prone positioning-in routine clinical practice for patients fulfilling the ARDS Berlin Definition. DESIGN, SETTING, AND PARTICIPANTS:The Large Observational Study to Understand the Global Impact of Severe Acute Respiratory Failure (LUNG SAFE) was an international, multicenter, prospective cohort study of patients undergoing invasive or noninvasive ventilation, conducted during 4 consecutive weeks in the winter of 2014 in a convenience sample of 459 ICUs from 50 countries across 5 continents. EXPOSURES:Acute respiratory distress syndrome. MAIN OUTCOMES AND MEASURES: The primary outcome was ICU incidence of ARDS. Secondary outcomes included assessment of clinician recognition of ARDS, the application of ventilatory management, the use of adjunctive interventions in routine clinical practice, and clinical outcomes from ARDS. RESULTS: Of 29,144 patients admitted to participating ICUs, 3022 (10.4%) fulfilled ARDS criteria. Of these, 2377 patients developed ARDS in the first 48 hours and whose respiratory failure was managed with invasive mechanical ventilation. The period prevalence of mild ARDS was 30.0% (95% CI, 28.2%-31.9%); of moderate ARDS, 46.6% (95% CI, 44.5%-48.6%); and of severe ARDS, 23.4% (95% CI, 21.7%-25.2%). ARDS represented 0.42 cases per ICU bed over 4 weeks and represented 10.4% (95% CI, 10.0%-10.7%) of ICU admissions and 23.4% of patients requiring mechanical ventilation. Clinical recognition of ARDS ranged from 51.3% (95% CI, 47.5%-55.0%) in mild to 78.5% (95% CI, 74.8%-81.8%) in severe ARDS. Less than two-thirds of patients with ARDS received a tidal volume 8 of mL/kg or less of predicted body weight. Plateau pressure was measured in 40.1% (95% CI, 38.2-42.1), whereas 82.6% (95% CI, 81.0%-84.1%) received a positive end-expository pressure (PEEP) of less than 12 cm H2O. Prone positioning was used in 16.3% (95% CI, 13.7%-19.2%) of patients with severe ARDS. Clinician recognition of ARDS was associated with higher PEEP, greater use of neuromuscular blockade, and prone positioning. Hospital mortality was 34.9% (95% CI, 31.4%-38.5%) for those with mild, 40.3% (95% CI, 37.4%-43.3%) for those with moderate, and 46.1% (95% CI, 41.9%-50.4%) for those with severe ARDS. CONCLUSIONS AND RELEVANCE: Among ICUs in 50 countries, the period prevalence of ARDS was 10.4% of ICU admissions. This syndrome appeared to be underrecognized and undertreated and associated with a high mortality rate. These findings indicate the potential for improvement in the management of patients with ARDS