Pulse sequences, Jeener Broekaert sequence

In some sequences, such as the FFC variety of the Jeener-Broekaert sequence, the RF pulses applied during the preparatory sub-sequence need to be coordinated in phase with those applied during the detection subsequence. In such cases the preparatory and detection sub-sequence sections of the FFC sequence are no longer mutually independent. 

The classical Jeener Broekaert sequence (133) is used to determine the dipolar-order relaxation time (in systems of spin 1/2 nuclides) and the Tiq relaxation time (in systems with spin 1 nuclides) of spin 1 nuclides with quadrupolar contributions to 7. Its FFC version is similar to the Inversion Recovery, except that the first 180° pulse is replaced by the sequence 90, — 5 — 45, the detection pulse becomes 45 and a special phase cycle is required. We shall not dwell on the details and purpose of the sequence since they go beyond the scope of this chapter. We wish to underline, however, the fact that sequences of this type require a close coordination of the preparatory sub-sequence with the signal-detection sub-sequence in order to isolate not just a particular magnetization component but a particular relaxation pathway. 

In the stimulated echo experiment, also shown in Fig. 6.2.3, the second pulse transfers the system into a mixture of Zeeman and double quantum order (alongandpg). Here, the relevant relaxation times are Ti (longitudinal Zeeman) and T q (double quantum), for which the 45 pulses of the Jeener-Broekaert sequence are replaced by 90v pulses. Again, two echos evolve at T] around the third pulse, and are refocussed by the fourth pulse. The two negative echo amplitudes vary as function of T2, with -[exp(-T2/Tiz) + exp(-T2/Ti3Q)], and both Ti and Tqq can be determined as separate values [14]. 

Fig. 5. Comparison of the frequency dependence of the total longitudinal proton relaxation time Ti and of the dipolar proton relaxation time Tto in the low-temperature nematic liquid crystal MBBA. r (v) was measured by the usual T] field-cycle with one B, r.f. pul%, shown by Rg. 1. Tto was measured by the usual Jeener-Broekaert sequence of three B r.f. pulses, in combination with a Bq field-cycle. which introduce an adjustable relaxation period between the second and third Bj pulse to give Tto(i )- The plots in the upper diagram show model fits according to equations (13a) 13d) with extensions described in the text. From the details at bottom about the experimental errors it can be clearly seen that the ratio T Tto significantly exceeds a value of 3 at medium frequencies, and in accordance with the model plot (frill line) approaches 1 in the low-frequency limit, where Bo is smaller than Bloc.

This is illustrated in Fig. 9. The 2D spectra refer to quadrupole echo sequences and characterize two possible reorientation mechanisms of a methyl group (three-site jumps vs continuous diffusion). Drastic spectral differences are observed. Ajqjarratly, these 2D relaxation spectra sensitively indicate the type of motion. The same is true for the corresponding normalized contour dots (see Fig. 9). We note that similar 2D spectra can be obtained from inversion recovery or Jeener-Broekaert sequences (see Fig. 6) [68]. Thus, by applying this 2D technique to different pulse sequoic, the various motions can be differentiated over an extremely wide dynamic range, extending from the fast-rotational to the ultraslow motional re me. Sin<% the different motions (see Fig. 4) modulate different kinds of molecular order (see Fig 3) these orders can be differentiated, likewise. 

Fig. 6. The generalized Jeener-Broekaert three pulse sequence. Note that FT of the solid echo and the alignment echo starts at times delayed by the pulse separation r, after the second and third pulse, respectively...

Li and Be work has gained from the application of the stimulated-echo spectroscopy to study the ultra-slow dynamics of nuclear spin-3/2 probes. Apart from the dominant first-order quadrupolar interaction, the impact of the homonuclear dipolar interactions was also considered. Explicit analytical expressions describing various aspects of a coupled quadupolar pair subjected to a Jeener-Broekaert pulse sequence have been derived. Extensions to larger spin systems are also briefly discussed. These results are compared with experimental data on a single-crystalline Li ion conductor. 

In the rotating reference frame spin-lock rates Fj p(SL) were measured with locking fields of 10 and 40 G. Below 170 K, decay of quadrupolar order was observed with Jeener-Broekaert pulse sequences. 

The Jeener-Broekaert (J-B) pulse sequence [2.18] shown in Fig. 2.5 allows the creation of spin alignment and the observation of a stimulated echo [2.19] for a spin-1 system. The density matrix at the end of second pulse... 

Jeener-Broekaert pulse sequence, 128-29 Karplus equation, 57,224 3-Lactam, 138-39... 

Jeener and Broekaert introduced, in 1%7, a three-pulse B,(r) sequence to measure the relaxation time Tm of the dipolar order of / = 1 spin systems in the presence of a conventional high Zeeman field, Bq, which is based on the decay time of the so-called Jeener echo . It was later extended by Spiess and Kemp-Harper and Wimperis to study in a similar way the quadrupolar order in / a 1 systems. The appearance of a Jeener echo depends upon the existence of interactions that are not averaged out by molecular motions on the considered time scale. The method has become of great importance in recent relaxation studies, in particular of liquid crystals because, in standard spin relaxation theories, it provides a power l means to separate and analyse the spectral densities / v) and /2) j. i4,is,2025 ggg... 

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