Effects of T2-relaxation in MAS NMR spectra of the satellite transitions for quadrupolar nuclei: a 27Al MAS and single-crystal NMR study of alum KAl(SO 4) 2 · 12H 2O

Abstract

Asymmetries in the manifold of spinning sidebands (ssbs) from the satellite transitions have been observed in variable-temperature 27Al MAS NMR spectra of alum (KAl(SO 4) 2 · 12H 2O), recorded in the temperature range from −76 to 92 °C. The asymmetries decrease with increasing temperature and reflect the fact that the ssbs exhibit systematically different linewidths for different spectral regions of the manifold. From spin-echo 27Al NMR experiments on a single-crystal of alum, it is demonstrated that these variations in linewidth originate from differences in transverse ( T 2) relaxation times for the two inner ( m = 1/2 ↔ m = 3/2 and m = −1/2 ↔ m = −3/2) and correspondingly for the two outer ( m = 3/2 ↔ m = 5/2 and m = −3/2 ↔ m = −5/2) satellite transitions. T 2 relaxation times in the range 0.5–3.5 ms are observed for the individual satellite transitions at −50 °C and 7.05 T, whereas the corresponding T 1 relaxation times, determined from similar saturation-recovery 27Al NMR experiments, are almost constant ( T 1 = 0.07–0.10 s) for the individual satellite transitions. The variation in T 2 values for the individual 27Al satellite transitions for alum is justified by a simple theoretical approach which considers the cross-correlation of the local fluctuating fields from the quadrupolar coupling and the heteronuclear ( 27Al– 1H) dipolar interaction on the T 2 relaxation times for the individual transitions. This approach and the observed differences in T 2 values indicate that a single random motional process modulates both the quadrupolar and heteronuclear dipolar interactions for 27Al in alum at low temperatures.