Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD

Guy A. Crundwell; Brett A. Cowans; Jeffrey A. Hopkins; John B. Grutzner; Bart Kahr

doi:10.1006/jssc.1999.8288

Vegard's Rule Revisited in Ba_xPb_1-x(NO₃)₂ by NMR and XRD

Guy A. Crundwell, Brett A. Cowans, Jeffrey A. Hopkins, John B. Grutzner, Bart Kahr

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Vegard's rule, originally based on powder X-ray diffraction data from Ba_xPb_1-x(NO₃)₂, is reevaluated through the application of nuclear magnetic resonance (NMR) spectroscopy. Solid state ²⁰⁷Pb NMR and ¹⁵N NMR spectra of Ba_xPb_1-x(NO₃)₂ (0.93>x>0.08) were recorded. The chemical shift dispersions for each magnetic nucleus are remarkable for their sensitivity to the nearest neighbor Pb²⁺ and Ba²⁺ distributions. The intensities of the peaks in the ²⁰⁷Pb spectra and their deviations from a simple binomial dependence reveal a non-statistical incorporation of Ba²⁺ and Pb²⁺ in the bulk crystals. Complementary analyses were performed by powder X-ray diffraction and with electron spectroscopy for chemical analysis that reveal bulk heterogeneities varying with crystal growth conditions. Vegard's original determination of a linear correlation between lattice constants and composition in Ba_xPb_1-x (NO₃)₂ is shown to have been a favorable consequence of the low resolution X-ray film methods available in the 1920s, but his additivity relationship is restored locally in the linear correlation of chemical shift with composition of the first metal coordination sphere.

Original language	English (US)
Pages (from-to)	327-335
Number of pages	9
Journal	Journal of Solid State Chemistry
Volume	145
Issue number	1
DOIs	https://doi.org/10.1006/jssc.1999.8288
State	Published - Jun 1999

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1006/jssc.1999.8288

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@article{b8936a9d32554fba9426e834c1a5d250,

title = "Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD",

abstract = "Vegard's rule, originally based on powder X-ray diffraction data from BaxPb1-x(NO3)2, is reevaluated through the application of nuclear magnetic resonance (NMR) spectroscopy. Solid state 207Pb NMR and 15N NMR spectra of BaxPb1-x(NO3)2 (0.93>x>0.08) were recorded. The chemical shift dispersions for each magnetic nucleus are remarkable for their sensitivity to the nearest neighbor Pb2+ and Ba2+ distributions. The intensities of the peaks in the 207Pb spectra and their deviations from a simple binomial dependence reveal a non-statistical incorporation of Ba2+ and Pb2+ in the bulk crystals. Complementary analyses were performed by powder X-ray diffraction and with electron spectroscopy for chemical analysis that reveal bulk heterogeneities varying with crystal growth conditions. Vegard's original determination of a linear correlation between lattice constants and composition in BaxPb1-x (NO3)2 is shown to have been a favorable consequence of the low resolution X-ray film methods available in the 1920s, but his additivity relationship is restored locally in the linear correlation of chemical shift with composition of the first metal coordination sphere.",

author = "Crundwell, {Guy A.} and Cowans, {Brett A.} and Hopkins, {Jeffrey A.} and Grutzner, {John B.} and Bart Kahr",

note = "Funding Information: We are grateful for {"}nancial support from the NSF (CHE-9727372, CHE-9457374) and the donors of the ACS-PRF (30688-AC), as well as the Department of Education for a National Needs Fellowship for J. H. We thank Professor Thomas Bein for access to his powder di!ractometer.",

year = "1999",

month = jun,

doi = "10.1006/jssc.1999.8288",

language = "English (US)",

volume = "145",

pages = "327--335",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Academic Press Inc.",

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T1 - Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD

AU - Crundwell, Guy A.

AU - Cowans, Brett A.

AU - Hopkins, Jeffrey A.

AU - Grutzner, John B.

AU - Kahr, Bart

N1 - Funding Information: We are grateful for "nancial support from the NSF (CHE-9727372, CHE-9457374) and the donors of the ACS-PRF (30688-AC), as well as the Department of Education for a National Needs Fellowship for J. H. We thank Professor Thomas Bein for access to his powder di!ractometer.

PY - 1999/6

Y1 - 1999/6

N2 - Vegard's rule, originally based on powder X-ray diffraction data from BaxPb1-x(NO3)2, is reevaluated through the application of nuclear magnetic resonance (NMR) spectroscopy. Solid state 207Pb NMR and 15N NMR spectra of BaxPb1-x(NO3)2 (0.93>x>0.08) were recorded. The chemical shift dispersions for each magnetic nucleus are remarkable for their sensitivity to the nearest neighbor Pb2+ and Ba2+ distributions. The intensities of the peaks in the 207Pb spectra and their deviations from a simple binomial dependence reveal a non-statistical incorporation of Ba2+ and Pb2+ in the bulk crystals. Complementary analyses were performed by powder X-ray diffraction and with electron spectroscopy for chemical analysis that reveal bulk heterogeneities varying with crystal growth conditions. Vegard's original determination of a linear correlation between lattice constants and composition in BaxPb1-x (NO3)2 is shown to have been a favorable consequence of the low resolution X-ray film methods available in the 1920s, but his additivity relationship is restored locally in the linear correlation of chemical shift with composition of the first metal coordination sphere.

AB - Vegard's rule, originally based on powder X-ray diffraction data from BaxPb1-x(NO3)2, is reevaluated through the application of nuclear magnetic resonance (NMR) spectroscopy. Solid state 207Pb NMR and 15N NMR spectra of BaxPb1-x(NO3)2 (0.93>x>0.08) were recorded. The chemical shift dispersions for each magnetic nucleus are remarkable for their sensitivity to the nearest neighbor Pb2+ and Ba2+ distributions. The intensities of the peaks in the 207Pb spectra and their deviations from a simple binomial dependence reveal a non-statistical incorporation of Ba2+ and Pb2+ in the bulk crystals. Complementary analyses were performed by powder X-ray diffraction and with electron spectroscopy for chemical analysis that reveal bulk heterogeneities varying with crystal growth conditions. Vegard's original determination of a linear correlation between lattice constants and composition in BaxPb1-x (NO3)2 is shown to have been a favorable consequence of the low resolution X-ray film methods available in the 1920s, but his additivity relationship is restored locally in the linear correlation of chemical shift with composition of the first metal coordination sphere.

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Vegard's Rule Revisited in Ba_xPb_1-x(NO₃)₂ by NMR and XRD

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