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Proton dynamics in letovicite: Part I. Static 1H and 15N NMR MAS experiments and lineshape simulations
-
Michael Fechtelkord
,
Astrid Diekmann
Published/Copyright:
April 1, 2015
Abstract
Synthetic letovicite (NH4)3H(SO4)2 has been investigated using 1H static, low-speed MAS, and 15N MAS NMR spectroscopy. Experiments were carried out in the temperature range of 215-425 K. The 1H MAS NMR spectra show three different resonances. The resonance assigned to the ammonia protons is broad and spinning sidebands cannot be resolved in the low-speed MAS NMR spectra. On the other hand, the acidic protons in the ferro- and paraphase show narrow signals with sideband patterns that enable a chemical shift anisotropy analysis. The chemical shift parameters of the free protons in the paraphase (δiso = 13.2 ppm, δaniso = 4.5 ppm, η = 0.0) differ completely from those of the protons in the ferrophase (δiso = 14.1 ppm, δaniso = 8.5 ppm, η = 1.0). The lowering of the chemical shift anisotropy δaniso by a factor of two and the change of the asymmetry parameter η imply a tetrahedral site jump mechanism of the protons. Three different ammonia tetrahedra can be distinguished by 15N MAS NMR spectroscopy in the P2/n phase below 273 K. Two resonances are prominent for the ferrophase (space group C2/c) corresponding to the two different crystallographic sites. Both resonances move together into a single resonance in the high-temperature phase that can be interpreted as fast dynamics of ammonia groups and its local environment so that the two crystallographic sites are locally nearly equal.
Keywords: Letovicite; proton conduction; ferroelastic; 1H; 15N; chemical shift anisotropy; lineshape analysis; reorientation; MAS; solid state NMR spectroscopy; phase transition
Received: 2006-3-23
Accepted: 2007-7-3
Published Online: 2015-4-1
Published in Print: 2007-11-1
© 2015 by Walter de Gruyter Berlin/Boston
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Keywords for this article
Letovicite;
proton conduction;
ferroelastic;
1H;
15N;
chemical shift anisotropy;
lineshape analysis;
reorientation;
MAS;
solid state NMR spectroscopy;
phase transition
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