Sr3CrN3: a new electride with partially filled d-shells

Electrides are ionic crystals in which the electrons prefer to occupy free space, serving as anions. Because the electrons prefer to be in the pockets, channels, or layers to the atomic orbitals around the nuclei, it has been challenging to find electrides with partially filled d-shells, since an unoccupied d-shell provides an energetically favourable location for the electrons to occupy. We recently predicted the existence of electrides with partially filled d-shells using high-throughput computational screening. Here, we provide an experimental support using X-ray absorption spectroscopy and X-ray and neutron diffraction to show that Sr3CrN3 is indeed an electride despite its partial d-shell configuration. Our findings indicate that Sr3CrN3 is the first known electride with a partially filled d-shell, in agreement with theory, which significantly broadens the criteria for the search for new electride materials

Powder diffraction methods for studies of borohydride-based energy storage materials

The world today is facing increasing energy demands and a simultaneous demand for cleaner and more environmentally friendly energy technologies. Hydrogen is recognized as a possible renewable energy carrier, but its large-scale utilization is mainly hampered by insufficient hydrogen storage capabilities. In this scenario, powder diffraction has a central position as the most informative and versatile technique available in materials science. This is illustrated in the present review by synthesis, physical, chemical and structural characterisation of novel boron based hydrides for hydrogen storage. Numerous novel BH4- based materials have been investigated during the past few years and this class of materials has a fascinating structural chemistry. The experimental methods presented can be applied to a variety of other material

High-pressure phase and transition phenomena in ammonia borane NH3BH3 from X-ray diffraction, Landau theory, and ab initio calculations

Structural evolution of a prospective hydrogen storage material, ammonia borane NH3BH3, has been studied at high pressures up to 12 GPa and at low temperatures by synchrotron powder diffraction. At 293 K and above 1.1 GPa a disordered I4mm structure reversibly transforms into a new ordered phase. Its Cmc21 structure was solved from the diffraction data, the positions of N and B atoms and the orientation of NH3 and BH3 groups were finally assigned with the help of density functional theory calculations. Group-theoretical analysis identifies a single two-component order parameter, combining ordering and atomic displacement mechanisms, which link an orientationally disordered parent phase I4mm with ordered distorted Cmc21, Pmn21 and P21 structures. We propose a generic phase diagram for NH3BH3, mapping three experimentally found and one predicted (P21) phases as a function of temperature and pressure, along with the evolution of the corresponding structural distortions. Ammonia borane belongs to the class of improper ferroelastics and we show that both temperature- and pressure-induced phase transitions can be driven to be of the second order. The role of N-H...H-B dihydrogen bonds and other intermolecular interactions in the stability of NH3BH3 polymorphs is examined.Comment: 23 pages, 7 figure

Versatile in situ powder X-ray diffraction cells for solid–gas investigations

Two multipurpose sample cells of quartz (SiO2) or sapphire (Al2O3) capillaries, developed for the study of solid–gas reactions in dosing or flow mode, are presented. They allow fast change of pressure up to 100 or 300 bar (1 bar = 100 000 Pa) and can also handle solid–liquid–gas studies

Topological metal behavior in GeBi2Te4 single crystals

The metallic character of the GeBi2Te4 single crystals is probed using a combination of structural and physical properties measurements, together with density functional theory (DFT) calculations. The structural study shows distorted Ge coordination polyhedra, mainly of the Ge octahedra. This has a major impact on the band structure, resulting in bulk metallic behavior of GeBi2Te4, as indicated by DFT calculations. Such calculations place GeBi2Te4 in a class of a few known non-trivial topological metals, and explains why an observed Dirac point lies below the Fermi energy at about -0.12eV. A topological picture of GeBi2Te4 is confirmed by the observation of surface state modulations by scanning tunneling microscopy (STM).Comment: 10 pages, 8 figure

New structural and magnetic aspects of the nanotube system Na2V3O7

We present new experimental results of low temperature x-ray synchrotron diffraction, neutron scattering and very low temperature (mK-range) bulk measurements on the nanotube system {\tube}. The crystal structure determined from our data is similar to the previously proposed model (P. Millet {\it et al.} J. Solid State Chem. $\bf{147}$, 676 (1999)), but also deviates from it in significant details. The structure comprises nanotubes along the c-axis formed by stacking units of two V-rings buckled in the $ab$-plane. The space group is P$\bar{3}$ and the composition is nonstoichiometric, Na(2-x)V3O7, x=0.17. The thermal evolution of the lattice parameters reveals anisotropic lattice compression on cooling. Neutron scattering experiments monitor a very weak magnetic signal at energies from -20 to 9 meV. New magnetic susceptibility, specific heat measurements and decay of remanent magnetization in the 30 mK - 300 mK range reveal that the previously observed transition at ~76 mK is spin-glass like with no long-range order. Presented experimental observations do not support models of isolated clusters, but are compatible with a model of odd-legged S=1/2 spin tubes possibly segmented into fragments with different lengths