Structural studies of ZrV2-xPxO7 solid solutions using P-31-{V-51} and V-51-{P-31} rotational echo double resonance NMR

被引:33
作者
Hudalla, C
Eckert, H
Dupree, R
机构
[1] UNIV CALIF SANTA BARBARA,DEPT CHEM,SANTA BARBARA,CA 93106
[2] UNIV WARWICK,DEPT PHYS,COVENTRY CV4 7AL,W MIDLANDS,ENGLAND
关键词
D O I
10.1021/jp960768z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
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页码:15986 / 15991
页数:6
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