Phonon Dispersion Analysis as an Indispensable Tool for Predictions of Solid State Polymorphism and Dynamic Metastability: Case of Compressed Silane

This work is dedicated to Prof. Russell J. Hemley in recognition of his seminal contributions to high pressure sciences Diamond anvil cell experiments suggest that upon compression above 26.5 GPa silane (SiH 4 ) forms a polymeric phase VI, whose crystal structure has not yet been solved. Here we present DFT calculations showing how phonon-guided optimization leads to a polymeric F dd2 structure which is the lowest-enthalpy polymorph of SiH 4 above 26.8 GPa, and which most probably can be identified as the experimentally observed polymeric phase. The new algorithm of predicting the lowest-energy structures enables simultaneous inspection of the potential energy surface of a given system, calculation of its vibrational properties, and assessment of chances for obtaining a metastable ambient-pressure structure via decompression. Our calculations indicate that at room temperature the differences in the vibrational and entropy terms contributing to the Gibbs free energy of different polymorphs of silane are negligible in comparison with corresponding differences in the zero-point energy corrections, in contrast to earlier suggestions. We also show that the F dd2 polymorph should be metastable upon decompression up to 5 GPa, which suggests the possibility of obtaining a polymeric ambient-pressure form of SiH 4 . Polymeric silane should exhibit facile thermal decomposition with evolution of molecular hydrogen and thus constitute an efficient (12.5 wt%) material for hydrogen storage

Real Space Observations of Magnesium Hydride Formation and Decomposition

The mechanisms of magnesium hydride formation and thermal decomposition are directly examined using in-situ imaging.Comment: 3 pages, 4 figure

Unexpected coexisting solid solutions in the quasi-binary Ag(II)F2/Cu(II)F2 phase diagram

High-temperature solid-state reaction between orthorhombic AgF2 and monoclinic CuF2 (y = 0.15, 0.3, 0.4, 0.5) in a fluorine atmosphere resulted in coexisting solid solutions of Cu-poor orthorhombic and Cu-rich monoclinic phases with stoichiometry Ag1-xCuxF2. Based on X-ray powder diffraction analyses, the mutual solubility in the orthorhombic phase (AgF2 doped with Cu) appears to be at an upper limit of Cu concentration of 30 mol % (Ag0.7Cu0.3F2), while the monoclinic phase (CuF2 doped with Ag) can form a nearly stoichiometric Cu : Ag = 1 : 1 solid solution (Cu0.56Ag0.44F2), preserving the CuF2 crystal structure. Experimental data and DFT calculations showed that AgF2 doped with Cu and CuF2 doped with Ag solid solutions deviate from the classical Vegards law. Magnetic measurements of Ag1-xCuxF2 showed that the Neel temperature (TN) decreases with increasing Cu content in both phases. Likewise, theoretical DFT+U calculations for Ag1-xCuxF2 showed that the progressive substitution of Ag by Cu decreases the magnetic interaction strength (J2D) in both structures. Electrical conductivity measurements of Ag0.85Cu0.15F2 showed a ca. 2-fold increase in specific ionic conductivity (3.71 x 10-13 plus/minus 2.6 x 10-15 S/cm) as compared to pure AgF2 (1.85 x 10-13 plus/minus 1.2 x 10-15 S/cm), indicating the formation of a vacancy- or F adatom-free metal difluoride sample.Comment: 9 pages, 4 figures, 1 Table, and electronic supplement of 14 page

Structure and Thermodynamics of the Mixed Alkali Alanates

The thermodynamics and structural properties of the hexahydride alanates (M2M'AlH6) with the elpasolite structure have been investigated. A series of mixed alkali alanates (Na2LiAlH6, K2LiAlH6 and K2NaAlH6) were synthesized and found to reversibly absorb and desorb hydrogen without the need for a catalyst. Pressure-composition isotherms were measured to investigate the thermodynamics of the absorption and desorption reactions with hydrogen. Isotherms for catalyzed (4 mol% TiCl3) and uncatalyzed Na2LiAlH6 exhibited an increase in kinetics, but no change in the bulk thermodynamics with the addition of a dopant. A structural analysis using synchrotron x-ray diffraction showed that these compounds favor the Fm-3m space group with the smaller ion (M') occupying an octahedral site. These results demonstrate that appropriate cation substitutions can be used to stabilize or destabilize the material and may provide an avenue to improving the unfavorable thermodynamics of a number of materials with promising gravimetric hydrogen densities.Comment: 6 pages, 7 figures,3 tables, submitted to PR

Flooding of Regular Phase Space Islands by Chaotic States

We investigate systems with a mixed phase space, where regular and chaotic dynamics coexist. Classically, regions with regular motion, the regular islands, are dynamically not connected to regions with chaotic motion, the chaotic sea. Typically, this is also reflected in the quantum properties, where eigenstates either concentrate on the regular or the chaotic regions. However, it was shown that quantum mechanically, due to the tunneling process, a coupling is induced and flooding of regular islands may occur. This happens when the Heisenberg time, the time needed to resolve the discrete spectrum, is larger than the tunneling time from the regular region to the chaotic sea. In this case the regular eigenstates disappear. We study this effect by the time evolution of wave packets initially started in the chaotic sea and find increasing probability in the regular island. Using random matrix models a quantitative prediction is derived. We find excellent agreement with numerical data obtained for quantum maps and billiards systems. For open systems we investigate the phenomenon of flooding and disappearance of regular states, where the escape time occurs as an additional time scale. We discuss the reappearance of regular states in the case of strongly opened systems. This is demonstrated numerically for quantum maps and experimentally for a mushroom shaped microwave resonator. The reappearance of regular states is explained qualitatively by a matrix model.Untersucht werden Systeme mit gemischtem Phasenraum, in denen sowohl reguläre als auch chaotische Dynamik auftritt. In der klassischen Mechanik sind Gebiete regulärer Bewegung, die sogenannten regulären Inseln, dynamisch nicht mit den Gebieten chaotischer Bewegung, der chaotischen See, verbunden. Dieses Verhalten spiegelt sich typischerweise auch in den quantenmechanischen Eigenschaften wider, so dass Eigenfunktionen entweder auf chaotischen oder regulären Gebieten konzentriert sind. Es wurde jedoch gezeigt, dass aufgrund des Tunneleffektes eine Kopplung auftritt und reguläre Inseln geflutet werden können. Dies geschieht wenn die Heisenbergzeit, das heißt die Zeit die das System benötigt, um das diskrete Spektrum aufzulösen, größer als die Tunnelzeit vom Regulären ins Chaotische ist, wobei reguläre Eigenzustände verschwinden. Dieser Effekt wird über eine Zeitentwicklung von Wellenpaketen, die in der chaotischen See gestartet werden, untersucht. Es kommt zu einer ansteigenden Wahrscheinlichkeit in der regulären Insel. Mithilfe von Zufallsmatrixmodellen wird eine quantitative Vorhersage abgeleitet, welche die numerischen Daten von Quantenabbildungen und Billardsystemen hervorragend beschreibt. Der Effekt des Flutens und das Verschwinden regulärer Zustände wird ebenfalls mit offenen Systemen untersucht. Hier tritt die Fluchtzeit als zusätzliche Zeitskala auf. Das Wiederkehren regulärer Zustände im Falle stark geöffneter Systeme wird qualitativ mithilfe eines Matrixmodells erklärt und numerisch für Quantenabbildungen sowie experimentell für einen pilzförmigen Mikrowellenresonator belegt

How inert, perturbing, or interacting are cryogenic matrices? A combined spectroscopic (infrared, electronic, and x-ray absorption) and DFT investigation of matrix-isolated Iron, Cobalt, Nickel, and Zinc Dibromides

The interactions of FeBr2, CoBr2, NiBr2 and ZnBr2 with Ne, Ar, Kr, Xe, CH4 and N2 matrices have been investigated using IR, electronic absorption and X-ray absorption spectroscopies, as well as DFT calculations. ZnBr2 is linear in all the matrices. NiBr2 is linear in all but N2 matrices where it is severely bent. For FeBr2 and CoBr2 there is a more gradual change, with evidence of non-linearity in Xe and CH4 matrices as well as N2. In the N2 matrices the presence of νNN modes blue shifted from the “free” N2 values indicates the presence of physisorbed species, and the magnitude of the blue-shift correlates with the shift in the ν3 mode of the metal dibromide. In the case of NiCl2 and NiBr2 chemisorbed species are formed after photolysis, but only if deposition takes place below 10 K. There was no evidence for chemisorbed species for NiF2 and FeBr2 and in the case of CoBr2 the evidence was not strong

Metal Hydrides and Related Materials - Energy Carriers for Novel Hydrogen and Electrochemical Storage

The seventh edition of the International Renewable and Sustainable Energy Conference (IRSEC) was held in Agadir (Sofitel Royal Bay, November 27–30, Morocco) under the Program Chair of Prof. Ahmed Ennaoui (IRESEN). IRSEC, as one of the biggest conferences in north Africa, aims at creating an international forum to facilitate discussions and exchanges in all aspects of renewable and sustainable energy. This Viewpoint will summarize the scientific presentations and stimulated discussions during the Special Session (November 28–29) on Metal Hydrides’ Energy covering topics of metal hydrides and energy related issues for innovative processes and technologies, with a focus on magnesium-based hydrides, intermetallic hydrides, complex and melt hydrides, porous materials, and thin films

Competing magnetostructural phases in a semiclassical system

The interplay between charge, structure, and magnetism gives rise to rich phase diagrams in complex materials with exotic properties emerging when phases compete. Molecule-based materials are particularly advantageous in this regard due to their low energy scales, flexible lattices, and chemical tunability. Here, we bring together high pressure Raman scattering, modeling, and first principles calculations to reveal the pressure-temperature-magnetic field phase diagram of Mn[N(CN)2]2. We uncover how hidden soft modes involving octahedral rotations drive two pressure-induced transitions triggering the low ??? high magnetic anisotropy crossover and a unique reorientation of exchange planes. These magnetostructural transitions and their mechanisms highlight the importance of spin-lattice interactions in establishing phases with novel magnetic properties in Mn(II)-containing systems