Manifestations of the absence of spin diffusion in multipulse NMR experiments on diluted dipolar solids

TL;DR

This paper explains long-lived spin echoes and asymmetries in multipulse NMR experiments on diluted dipolar solids, attributing these phenomena to stimulated echoes caused by rf inhomogeneity and lack of spin diffusion.

Contribution

It provides a comprehensive explanation for anomalies in multipulse NMR, linking stimulated echoes to specific experimental conditions and sequence phases, supported by both experiments and theory.

Findings

Stimulated echoes cause long magnetization tails.

Constructive or destructive interference depends on pulse phase alternation.

Even-odd asymmetry arises from stimulated echo contributions.

Abstract

Puzzling anomalies previously observed in multipulse NMR experiments in natural abundance 29Si [A.E. Dementyev, D. Li, K. MacLean, and S.E. Barrett, Phys. Rev. B 68, 153302 (2003)] such as long-lived spin echoes and even-odd asymmetries, are also found in polycrystalline C60. Further experiments controlling the phases and tilting angles of the pulse trains, as well as analytical and numerical calculations allowed us to explain the origin of these anomalies. We prove that the observation of long magnetization tails requires two conditions: i) an rf field inhomogeneity able to produce different tilting angles in different sites of the sample and ii) the absence of spin diffusion (non-effective flip-flop interactions). The last requirement is easily satisfied in diluted dipolar solids, where the frequency differences between sites, caused by disorder or other sources, are usually at least one order of magnitude larger than the dipolar couplings. Both conditions lead to the generation of stimulated echoes in Carr-Purcell (CP) and Carr-Purcell-Meiboom-Gill (CPMG) pulse trains. We show, both experimentally and theoretically, that the stimulated echoes interfere constructively or destructively with the normal (Hahn) echoes depending on the alternation or not of the pi pulse phases in the CP and the CPMG sequences. Constructive interferences occur for the CP and CPMG sequences with and without phase alternation respectively, which are the cases where long magnetization tails are observed. Sequences with two, three and four pi pulses after the pi/2 pulse allow us to disentangle the contributions of the different echoes and show how the stimulated echoes originate the even-odd asymmetry observed in both 29Si and C60 polycrystalline samples.