High-pressure single-crystal X-ray diffraction study of katoite hydrogarnet: Evidence for a phase transition from Ia3d → I4̄3d symmetry at 5 GPa

George A. Lager, Robert T Downs, Marcus Origlieri, Rebecca Garoutte

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The crystal structure of katoite hydrogarnet has been refined at 0.0001, 2.15, 4.21, 5.09, 6.00, 7.09, and 7.78 GPa from single-crystal X-ray diffraction data using a 4:1 methanol: ethanol mixture as pressure medium in a Merrill-Bassett diamond-anvil cell. Below ~5 GPa, the katoite structure has la3d symmetry and compresses by bond shortening rather than bond bending, in agreement with recent quantum mechanical calculations. An unconstrained third-order Birch-Murnaghan fit to the unit-cell volumes and pressures for la3d symmetry gave the following equation of state parameters: Vo = 1987.6(1) Å3, Ko = 58(1) GPa and K' = 4.0(7). Above this pressure, the structure undergoes a phase transition to space group I43d, a non-centric subgroup of la3d. In the I43d structure. there are two non-equivalent (O4H4) groups. Both the Ca and Al atoms are displaced along a relative to their positions in la3d. It is proposed that compression of the short H-H distance between (O4H4) groups destabilizes the structure and may initiate the observed phase transition. Corroboration of this model will require accurate information on the hydrogen atom positions at pressures above 5 GPa.

Original languageEnglish (US)
Pages (from-to)642-647
Number of pages6
JournalAmerican Mineralogist
Volume87
Issue number5-6
StatePublished - 2002
Externally publishedYes

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Crystal symmetry
phase transition
symmetry
Phase transitions
X-ray diffraction
Single crystals
crystal
X ray diffraction
single crystals
diffraction
x rays
Atoms
diamond anvil cell
Diamond
anvils
subgroups
cells
Equations of state
equation of state
crystal structure

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

High-pressure single-crystal X-ray diffraction study of katoite hydrogarnet : Evidence for a phase transition from Ia3d → I4̄3d symmetry at 5 GPa. / Lager, George A.; Downs, Robert T; Origlieri, Marcus; Garoutte, Rebecca.

In: American Mineralogist, Vol. 87, No. 5-6, 2002, p. 642-647.

Research output: Contribution to journalArticle

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abstract = "The crystal structure of katoite hydrogarnet has been refined at 0.0001, 2.15, 4.21, 5.09, 6.00, 7.09, and 7.78 GPa from single-crystal X-ray diffraction data using a 4:1 methanol: ethanol mixture as pressure medium in a Merrill-Bassett diamond-anvil cell. Below ~5 GPa, the katoite structure has la3d symmetry and compresses by bond shortening rather than bond bending, in agreement with recent quantum mechanical calculations. An unconstrained third-order Birch-Murnaghan fit to the unit-cell volumes and pressures for la3d symmetry gave the following equation of state parameters: Vo = 1987.6(1) {\AA}3, Ko = 58(1) GPa and K' = 4.0(7). Above this pressure, the structure undergoes a phase transition to space group I43d, a non-centric subgroup of la3d. In the I43d structure. there are two non-equivalent (O4H4) groups. Both the Ca and Al atoms are displaced along a relative to their positions in la3d. It is proposed that compression of the short H-H distance between (O4H4) groups destabilizes the structure and may initiate the observed phase transition. Corroboration of this model will require accurate information on the hydrogen atom positions at pressures above 5 GPa.",
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