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Title: High-pressure phase transition of alkali metal–transition metal deuteride Li 2 PdD 2

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGNDARPA
OSTI Identifier:
1368302
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 146; Journal Issue: 23
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Yao, Yansun, Stavrou, Elissaios, Goncharov, Alexander F., Majumdar, Arnab, Wang, Hui, Prakapenka, Vitali B., Epshteyn, Albert, and Purdy, Andrew P. High-pressure phase transition of alkali metal–transition metal deuteride Li 2 PdD 2. United States: N. p., 2017. Web. doi:10.1063/1.4986245.
Yao, Yansun, Stavrou, Elissaios, Goncharov, Alexander F., Majumdar, Arnab, Wang, Hui, Prakapenka, Vitali B., Epshteyn, Albert, & Purdy, Andrew P. High-pressure phase transition of alkali metal–transition metal deuteride Li 2 PdD 2. United States. doi:10.1063/1.4986245.
Yao, Yansun, Stavrou, Elissaios, Goncharov, Alexander F., Majumdar, Arnab, Wang, Hui, Prakapenka, Vitali B., Epshteyn, Albert, and Purdy, Andrew P. Wed . "High-pressure phase transition of alkali metal–transition metal deuteride Li 2 PdD 2". United States. doi:10.1063/1.4986245.
@article{osti_1368302,
title = {High-pressure phase transition of alkali metal–transition metal deuteride Li 2 PdD 2},
author = {Yao, Yansun and Stavrou, Elissaios and Goncharov, Alexander F. and Majumdar, Arnab and Wang, Hui and Prakapenka, Vitali B. and Epshteyn, Albert and Purdy, Andrew P.},
abstractNote = {},
doi = {10.1063/1.4986245},
journal = {Journal of Chemical Physics},
number = 23,
volume = 146,
place = {United States},
year = {Wed Jun 21 00:00:00 EDT 2017},
month = {Wed Jun 21 00:00:00 EDT 2017}
}
  • Li{sub 2}PtH{sub 6}, the missing member of the complex transition metal hydride series A{sub 2}PtH{sub 6} (A=alkali metal), was prepared by reacting mixtures of LiH and Pt in the presence of BH{sub 3}NH{sub 3} as hydrogen source at pressures above 8 GPa. According to powder X-ray diffraction analysis, Li{sub 2}PtH{sub 6} is isostructural to its heavier homologues and crystallizes in the cubic K{sub 2}PtCl{sub 6} structure (space group Fm3-bar m, a=6.7681(3), Z=4). However, PtH{sub 6}{sup 2-} octahedral complexes in Li{sub 2}PtH{sub 6} approach each other closely and its structure may likewise be regarded as a defective perovskite structure where halfmore » of the octahedrally coordinated atoms (cations) are missing. The IR spectrum of Li{sub 2}PtH{sub 6} reveals the Pt-H T{sub 1u} stretch and bend at 1840 and 889 cm{sup -1}, respectively. - Graphical abstract: Li{sub 2}PtH{sub 6}, the missing start member of the complex metal hydride series A{sub 2}PtH{sub 6} (A=alkali metal) has been prepared by high pressure hydrogenation. In contrast to the heavier homologues, PtH{sub 6}{sup 2-} octahedral units in Li{sub 2}PtH{sub 6} are not well separated and H atoms form a substructure closely corresponding to that of O atoms in cubic perovskite.« less
  • The new lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P2{sub 1}/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li{sub 2}Pd{sub 3}S{sub 4} and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li{sub 2}Pt{sub 3}S{sub 4}. The crystal structures are built up from two distinct Pd/Pt sites, one of whichmore » is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS{sub 4}/PtS{sub 4} units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS{sub 4}/PtS{sub 4} units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu{sub 2}Pd{sub 3}Se{sub 4} and chrisstanleyite, Ag{sub 2}Pd{sub 3}Se{sub 4}, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state {sup 7}Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites. - Graphical abstract: The ternary lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were prepared via multianvil high-pressure/high-temperature syntheses. They are built up from square planar PtS{sub 4}/PdS{sub 4} units with lithium located in the channels of the crystal structure. - Highlights: • Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are the missing sulfide analogue compounds to Cu{sub 2}Pd{sub 3}Se{sub 4} and Ag{sub 2}Pd{sub 3}Se{sub 4}. • The compounds are the first Pd or Pt containing lithium transition-metal sulfides. • Li mobility was investigated via temp. dependent XRD and solid state {sup 7}Li NMR. • Magnetic properties revealed Pauli paramagnetic or diamagnetic contributions.« less
  • This paper reports on various titanium and palladium metal and hydride preparations subjected to D{sub 2} gas loading at pressures up to 2.4 kbars followed by temperature cycling. Neutron yield was monitored in an underground laboratory with a detection system with a counting efficiency of {approximately}9.2% and a background of 10 count/h. No clearly identified neutron yield in excess of background has been detected.
  • Based on the 4,4'-bipyridine organic linker, metal–organic frameworks of Co 2(4,4'-bpy) 3(NO 3) 4·xH 2O (CB-MOF) have been prepared. The pressure-dependent structure evolution of CB-MOF has been investigated up to 11 GPa. An isostructural phase transition was observed at about 6 GPa followed by negative compressibility along the b axis.