Single crystal X-ray diffraction study of a mixed-valence gold compound, Cs{sub 2}Au{sup I}Au{sup III}Cl{sub 6} under high pressures up to 18 GPa: Pressure-induced phase transition coupled with gold valence transition

Journal Article · Sun Apr 15 04:00:00 EDT 2007 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2007.01.037· OSTI ID:21015784

Matsushita, Nobuyuki ^[1]; Ahsbahs, Hans ^[1]; Hafner, Stefan S ^[1]; Kojima, Norimichi ^[2]

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1. Institute of Mineralogy, University of Marburg, Marburg 35032 (Germany)
2. Department of Basic Science, Graduate School of Arts and Sciences, University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8902 (Japan)

We performed the single-crystal X-ray diffraction study of a perovskite-type gold mixed-valence compound, Cs{sub 2}Au{sup I}Au{sup III}Cl{sub 6}, under high pressures up to 18 GPa by using a diamond-anvil-cell with helium gas as an ideal hydrostatic pressure-transmitting medium. The lattice parameters and the variable atomic positional parameters were obtained with reasonable accuracy at various pressures. A structural phase transition at ca. 12.5 GPa from I4/mmm to Pm3m was found. The lattice parameters a {sub 0} and c {sub 0}, denoted in the tetragonal cell setting, result in the relationship 2{sup 1/2} a {sub 0}=c {sub 0}, and the superstructure reflections h k l (l is odd), caused by the shift of the Cl ions from the midpoint of the Au ions, disappeared at pressures above the phase transition. Both elongated [Au{sup III}Cl{sub 6}] and compressed [Au{sup I}Cl{sub 6}] octahedra in the low-pressure phase smoothly approach regular octahedra with increasing pressure. Above the structural phase transition at 12.5 GPa, all the [AuCl{sub 6}] octahedra are crystallographically equivalent, which shows that the tetragonal-to-cubic phase transition accompanies the valence transition from the Au{sup I}/Au{sup III} mixed-valence state to the Au{sup II} single-valence state. - Graphical abstract: Single-crystal X-ray diffraction study under high pressures up to 18 GPa by using a diamond-anvil-cell with helium gas as an ideal hydrostatic pressure medium has revealed that a perovskite-type gold mixed-valence compound, Cs{sub 2}Au{sup I}Au{sup III}Cl{sub 6}, exhibits the structural phase transition from tetragonal to cubic at 12.5 GPa accompanying gold valence transition.

• OSTI ID: 21015784
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 4 Vol. 180; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CESIUM COMPOUNDS
CHLORINE IONS
CRYSTAL-PHASE TRANSFORMATIONS
CUBIC LATTICES
GOLD COMPLEXES
GOLD COMPOUNDS
LATTICE PARAMETERS
MONOCRYSTALS
PEROVSKITE
PRESSURE RANGE GIGA PA
TETRAGONAL LATTICES
X-RAY DIFFRACTION