The anti-perovskite type hydride InPd{sub 3}H{sub 0.89}

• Published in: Journal of solid state chemistry Vol. 183; no. 10
• Main Authors: Kohlmann, H., Skripov, A.V., Soloninin, A.V., Udovic, T.J.
• Format: Journal Article
• Language: English
• Published: United States 15-10-2010
• Subjects: BARYON REACTIONS; CHEMICAL REACTIONS; COHERENT SCATTERING; CRYSTAL DEFECTS; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CUBIC LATTICES; DEUTERIDES; DEUTERIUM COMPOUNDS; DIFFRACTION; ELEMENTS; HADRON REACTIONS; HYDRIDES; HYDROGEN COMPOUNDS; HYDROGENATION; INDIUM COMPOUNDS; INELASTIC SCATTERING; INTERSTITIALS; MATERIALS SCIENCE; METALS; MINERALS; NEUTRON DIFFRACTION; NEUTRON REACTIONS; NMR SPECTRA; NUCLEAR REACTIONS; NUCLEON REACTIONS; OXIDE MINERALS; PALLADIUM; PALLADIUM COMPOUNDS; PALLADIUM HYDRIDES; PEROVSKITE; PEROVSKITES; PLATINUM METALS; POINT DEFECTS; SCATTERING; SPACE GROUPS; SPECTRA; SYMMETRY GROUPS; TEMPERATURE RANGE; TEMPERATURE RANGE 0013-0065 K; TEMPERATURE RANGE 0273-0400 K; TRANSITION ELEMENT COMPOUNDS; TRANSITION ELEMENTS; VOIDS
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2010.08.015

Hydrogenation of tetragonal InPd{sub 3} in the ZrAl{sub 3} type structure (four-fold ccp superstructure) yields a hydride with a cubic AuCu{sub 3} type structure (one-fold ccp superstructure). Deuterium can be located by neutron powder diffraction in octahedral voids surrounded exclusively by palladium, [Pd{sub 6}], which are 88.5(6)% occupied in a statistical manner. The resulting deuteride InPd{sub 3}D{sub 0.89} thus crystallizes in a cubic anti-perovskite type structure (space group Pm3-bar m (no. 221), a=402.25(1) pm at 299(2) K). The Pd-D distance of 201.13(1) pm is typical for interstitial hydrides with palladium. Inelastic neutron scattering on the hydride InPd{sub 3}H{sub 0.89}, which shows a spectrum similar to that of binary palladium hydride, confirms the cubic site symmetry of hydrogen in [Pd{sub 6}] interstices. This is also confirmed by the absence of any quadrupole splitting in the {sup 2}D-NMR signal of the deuteride. {sup 1}H NMR spectra of InPd{sub 3}H{sub 0.89} do not show any motional narrowing. Values found for the H jump rate {tau}{sup -1} in InPd{sub 3}H{sub 0.89} remain below 10{sup 6} s{sup -1} in the studied temperature range 28-360 K, indicating a small hydrogen mobility in InPd{sub 3}H{sub 0.8} as compared with binary palladium hydride, PdH{sub {<=}1}. This can be attributed to the large spatial separation of the [Pd{sub 6}] sites. - Graphical abstract: Hydrogen induces a rearrangement in InPd{sub 3} from a ZrAl{sub 3} type structure to a cubic AuCu{sub 3} type structure, thus forming an anti-perovskite type hydride InPd{sub 3}H{sub 0.89}.