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Hydrogenation-Induced Structure and Property Changes in the Rare-Earth Metal Gallide NdGa: Evolution of a [GaH](2-) Polyanion Containing Peierls-like Ga-H Chains
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
Inst Energy Technol, Phys Dept, NO-2027 Kjeller, Norway..
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2016 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 55, no 1, 345-352 p.Article in journal (Refereed) PublishedText
Abstract [en]

The hydride NdGaH1+x (x approximate to 0.66) and its deuterized analogue were obtained by sintering the Zintl phase NdGa with the CrB structure in a hydrogen atmosphere at pressures of 10-20 bar and temperatures near 300 degrees C. The system NdGa/NdGaH1+x exhibits reversible H storage capability. H uptake and release were investigated by kinetic absorption measurements and thermal desorption mass spectroscopy, which showed a maximum H concentration corresponding to "NdGaH2" (0.93 wt % H) and a two-step desorption process, respectively. The crystal structure of NdGaH1+x was characterized by neutron diffraction (P2(1)/m, a = 4.1103(7), b = 4.1662(7), c = 6.464(1) angstrom, beta = 108.61(1)degrees Z = 2). H incorporates in NdGa by occupying two distinct positions, H1 and H2. HI is coordinated in a tetrahedral fashion by Nd atoms. The H2 position displays flexible occupancy, and H2 atoms attain a trigonal bipyramidal coordination by centering a triangle of Nd atoms and bridging two Ga atoms. The phase stability and electronic structure of NdGaH1+x, were analyzed by first-principles DFT calculations. NdGaH1H2 (NdGaH2) may be expressed as Nd3+(H1(-)[GaH2](2-). The two-dimensional polyanion [GaH](2-) features linear -H-Ga-H-Ga- chains with alternating short (1.8 A) and long (2.4 angstrom) Ga-H distances, which resembles a Peierls distortion. H2 deficiency (x < 1) results in the fragmentation of chains. For x = 0.66 arrangements with five-atom moieties, Ga-H-Ga-H-Ga are energetically most favorable. From magnetic measurements, the Curie-Weiss constant and effective magnetic moment of NdGaH1.66 were obtained. The former indicates antiferromagnetic interactions, and the latter attains a value of similar to 3.6 mu(B), which is typical for compounds containing Nd3 ions.

Place, publisher, year, edition, pages
2016. Vol. 55, no 1, 345-352 p.
National Category
Inorganic Chemistry Engineering and Technology
URN: urn:nbn:se:uu:diva-275549DOI: 10.1021/acs.inorgchem.5b02485ISI: 000367706100042OAI: oai:DiVA.org:uu-275549DiVA: diva2:900626
EU, FP7, Seventh Framework Programme, 284522Swedish Research Council
Available from: 2016-02-04 Created: 2016-02-04 Last updated: 2016-08-26Bibliographically approved
In thesis
1. Metal Hydrogen Interaction and Structural Characterization of Amorphous Materials from first principles
Open this publication in new window or tab >>Metal Hydrogen Interaction and Structural Characterization of Amorphous Materials from first principles
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, first-principles calculations based on density functional theory have been employed to investigate metal hydrogen interaction in transition, p-block and rare earth metals. Furthermore, the accuracy of the stochastic quenching method was tested in describing the structure of amorphous Fe(1-x)Zrx.

The investigated systems of transition metal hydrides are V-H and ScZr(CoNi)2-H. For V-H, the main focus of the studies is the effect that strain has on the potential energy landscape which governs the metal hydrogen interactions. The investigation has focused on how the properties of hydrogen occupancy in the interstitial sites changes with strain and also how the hydrogen atoms themselves exert strain on the vanadium structure to lower the energy. Results on diffusion, induced strain and zero-point energy are presented which all reveal the considerable difference between tetrahedral and octahedral site occupancy. Diffusion was studied by employing ab initio molecular dynamics simulations to obtain diffusion coefficients and to map the movement of the hydrogen atom. A description of hydrogen in vanadium is provided from a fundamental basis that is expected to be applicable to any lattice gas system. For ScZr(CoNi)2-H, the difference of hydrogen occupancy in various interstitial sites and the hydrogen-induced strain was also investigated through calculations of the change in total volume as a function of hydrogen concentration.

The fundamental properties of metal hydrogen bonding were investigated by studying the Zintl phase hydrides that are constituted of the electropositive metal of Nd or Gd and the electronegative metal Ga. Mixing metals of very different electronegativity gives rise to an intricate potential energy landscape in which the incorporation of hydrogen will have a big effect on both the electronic and atomic structure. From the theoretical side of the investigation, structural parameters are presented along with the density of states and Bader charge analysis to describe the hydrogen induced changes to the atomic and electronic structures.

Finally, the accuracy of the stochastic quenching method in describing amorphous Fe(1-x)Zrx was evaluated by comparing simulated and measured EXAFS spectra. Once the structural agreement had been established the simulated structures were characterized through radial distribution functions and an analysis of the short-range order from Voronoi tessellation. The structural changes with respect to the composition parameter x were also evaluated.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2016. 72 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1396
hydrogen, vanadium, zintl, laves, strain, diffusion, amorphous, dft, molecular dynamics, md
National Category
Condensed Matter Physics
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
urn:nbn:se:uu:diva-299940 (URN)978-91-554-9635-7 (ISBN)
External cooperation:
Public defence
2016-09-28, Å80127, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Available from: 2016-08-31 Created: 2016-07-29 Last updated: 2016-09-05

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Johansson, RobertSarkar, TapatiAndersson, Mikael S.Nordblad, PerScheicher, Ralph H.Sahlberg, Martin
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