Enhancing the central-transition NMR signal of quadrupolar nuclei by spin population transfer using SW-FAM pulse trains with a tangent-shaped sweep profile

摘要

Solid-state NMR of quadrupolar nuclei with half-integer spin, such as ~(25)Mg (I=5/2) or ~(43)Ca (I=7/2), suffers from low sensitivity, which may be improved using spin population transfer (SPT) from the satellite transitions. Effecting SPT with good efficiency is especially challenging under static conditions, and several techniques such as double-frequency sweeps (DFS), hyperbolic secant pulses (HS) and frequency-swept fast-amplitude modulated pulses (SW-FAM) have been suggested for achieving the necessary manipulations of the satellite transitions. We here investigate the SPT properties of an SWFAM sequence with a tangent-shaped profile. The new SW(tan)-FAM pulse train is shown to possess superior SPT performance to the SW(1/τ)-FAM sequence, which hitherto has been considered to be the best FAM method for signal enhancement of static spectra, by both numerical simulations on a ~(27)Al model system, and experimental results on aluminium acetyl acetonate, Al(acac)_3. In addition, the CT enhancement of individual crystallites from the polycrystalline sample with a defined angle between principal z-axis of the diagonal Q-tensor and the external field was considered by numerical simulations. In the vicinity of the magic angle θ_m = 54.7°, a region of zero enhancement exists. Use of the SW(tan)-FAM sequence allows extending the frequency sweep further into this region, with beneficial effects for the overall enhancement and the faithfulness of the line shape. In agreement with previously published studies, our numerical simulations on SPT for single crystals again evidence that the enhancement factors for a polycrystalline sample range from zero enhancement to the maximum gain of 21, with the total enhancement factor of the full powder pattern being the summation of these strongly varying individual factors. This variation is the cause for line shape distortions in SPT-enhanced spectra. At the same time, these findings prove the capability of frequency sweeps (i.e., DFS and SW-FAM) to fully invert the satellite transitions under certain conditions.