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1.
Solid State Nucl Magn Reson ; 34(1-2): 32-6, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-18547790

RESUMO

It is commonplace that NMR echo maxima appear at times for which the dephasing and the rephasing periods of a pulse sequence are equally long. However, for stimulated echoes a significant time shift from this naively expected echo position can be observed if the dephasing times are smaller than the inverse line width of the NMR spectrum. This effect, which will be observable for any line shape, is evaluated quantitatively for Gaussian and for Pake-like patterns. Comparison of the calculations is made with experimental results from (6)Li- and from (2)H-NMR and excellent agreement is found. In the simultaneous presence of broad and narrow lines, the apparent time shift can give rise to characteristic distortions in spin-alignment spectra. This explains some features previously observed using (7)Li-NMR.

2.
Phys Chem Chem Phys ; 8(3): 369-78, 2006 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-16482280

RESUMO

The relation between structure and ion dynamics in the three polymorphs of Ag(5)Te(2)Cl has been investigated using (109)Ag, (125)Te, and (35)Cl NMR spectroscopies. Specifically, the influence of the structural phase transitions observed near 240 K (P2(1)/c<-->P2(1)/n) and near 332 K (P2(1)/n<-->I4/mcm) upon silver ion mobilities has been studied by temperature dependent (109)Ag NMR lineshapes and spin-lattice relaxation times. While the superionic high temperature phase alpha-Ag(5)Te(2)Cl is characterized by a molten cationic sublattice, fast ion dynamics in the medium-temperature phase beta-Ag(5)Te(2)Cl occurs in spatially restricted regions comprising all the crystallographically distinct silver sites. Temperature dependent magic-angle-spinning linewidths yield an activation energy of 0.38 eV, consistent with 0.44 eV measured from dc electric conductivities. For the low-temperature gamma-modification, results of two- and three-time (109)Ag correlation spectroscopies provide a detailed insight into the nature of the silver ionic hopping motion. Temperature dependent jump rates measured by two-time correlation functions yield an activation energy E(a)= 0.48 eV. (109)Ag NMR three-time correlation functions indicate that the non-exponential relaxation behavior of the silver ions can be attributed to a broad distribution of jump rates rather than correlated forward-backward jumps. Nevertheless, all the silver ions are mobile down to temperatures of about 185 K.


Assuntos
Cloro/química , Prata/química , Telúrio/química , Cátions/química , Cátions/metabolismo , Simulação por Computador , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética/métodos , Modelos Químicos , Prata/metabolismo , Telúrio/metabolismo , Temperatura , Termodinâmica
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