An alternative structure of Pu{sub 4}O{sub 9} (''PuO{sub 2.25}'') incorporating interstitial hydroxyl rather than oxide

Bond length/bond strength relationships are applied to the Pu{sub 4}O{sub 9} ('PuO{sub 2.25}') structure proposed by others and support one Pu(V) with a central hydroxyl ion but not a central oxide ion nor formation of Pu(VI). Bond distances and bond strengths are normal for a central ion...

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Bibliographic Details
Published in:Journal of solid state chemistry 2005-02, Vol.178 (2)
Main Authors: Penneman, R.A., Paffett, M.T.
Format: Article
Language:English
Subjects:
ABSORPTION SPECTROSCOPY
ANIONS
BOND LENGTHS
FINE STRUCTURE
HYDROXIDES
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
LATTICE PARAMETERS
PLUTONIUM OXIDES
VALENCE
X-RAY PHOTOELECTRON SPECTROSCOPY
X-RAY SPECTROSCOPY
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Summary:Bond length/bond strength relationships are applied to the Pu{sub 4}O{sub 9} ('PuO{sub 2.25}') structure proposed by others and support one Pu(V) with a central hydroxyl ion but not a central oxide ion nor formation of Pu(VI). Bond distances and bond strengths are normal for a central ion of unit charge, and reconcile the finding that cell dimensions are so minimally changed from those of PuO{sub 2}. Substitution of hydroxyl for oxide accounts for the 'excess' oxygen content of PuO{sub 2.265,} yielding PuO{sub 2}(OH){sub 0.249.} The short range, local order (structure) of the 'Pu{sub 4}O{sub 9}' entity is alternatively formulated as Pu{sub 4}O{sub 8}OH.
ISSN:0022-4596
1095-726X
DOI:10.1016/j.jssc.2004.08.022