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Structural studies of ZrV2-xPxO7 solid solutions using P-31-{V-51} and V-51-{P-31} rotational echo double resonance NMR
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UNSPECIFIED (1996) Structural studies of ZrV2-xPxO7 solid solutions using P-31-{V-51} and V-51-{P-31} rotational echo double resonance NMR. JOURNAL OF PHYSICAL CHEMISTRY, 100 (39). pp. 15986-15991. ISSN 0022-3654.
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Abstract
The negative thermal expansion coefficients of ZrV2-xPxO7 solid solutions are attributed to the structural flexibility of M-O-M' dimers (M, M' = P, V), upon which the structure of these materials is based. The local environments of these M species have been probed by high-resolution P-31 and V-51 solid state NMR experiments, assisted by V-51-{P-31} and P-31-{V-51} rotational echo double resonance (REDOR) studies for assignment purposes. At all of the compositions studied, formation of mixed P-O-V dimers is distinctly preferred over the symmetric P-O-P and V-O-V species, indicative of chemical ordering. Analysis of the REDOR experiments, assuming simple spin 1/2 behavior of the V-51 nuclei, yields an estimate of the P ... V internuclear distance in the mixed dimers of 3.42 Angstrom, consistent with a linear geometry of the P-O-V units as required by the space group symmetry. This result is subject to the important caveat that a precise theoretical description of REDOR behavior involving quadrupolar nuclei is not yet available.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF PHYSICAL CHEMISTRY | ||||
Publisher: | AMER CHEMICAL SOC | ||||
ISSN: | 0022-3654 | ||||
Official Date: | 26 September 1996 | ||||
Dates: |
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Volume: | 100 | ||||
Number: | 39 | ||||
Number of Pages: | 6 | ||||
Page Range: | pp. 15986-15991 | ||||
Publication Status: | Published |
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