Stimulated-echo decays

Figure 39. 31P NMR stimulated-echo decays of m-tricresyl phosphate (m-TCP, Ts = 214K) at...

To measure the longitudinal relaxation time Ti, an inversion or saturation pulse is applied, followed, after a variable time T, by a two-pulse echo experiment for detection (Fig. 5b). The inversion or saturation pulse induces a large change of the echo amplitude for T < T. With increasing T, the echo amphtude recovers to its equilibriiun value with time constant Ti. The echo amphtude of the stimulated echo (Fig. 5c) decays with time constant T2 when the interpulse delay T is incremented, and with the stimulated-echo decay time constant Tse < T1 when the interpulse delay T is incremented. A faster decay, compared to inversion or saturation recovery experiments, can arise from spectral diffusion, because of a change of the resonance frequency for the observed spins, of the order of Av = 1/t on the time scale of T. Quantitative analysis of spectral diffusion can provide information on the reorientation dynamics of the paramagnetic centers. 

Spin dynamic studies, including saturation and inversion recovery, Hahn echo and stimulated echo decay, as well as Carr-Purcell-Meiboom-Gill sequences, can be performed, yielding relaxation times. When rapid reaction kinetics are being measured, information is also gained on transient phenomena such as chemically induced electron polarization (CIDEP). 

However, this model is inconsistent with both the CW ESR spectra and data from stimulated echo decay. 

The stimulated (tln-ee-pulse) echo decay may also be modulated, but only by the nuclear frequencies (0,2 and... 

The main advantage of tlie tln-ee-pulse ESEEM experiment as compared to the two-pulse approach lies m the slow decay of the stimulated echo intensity detemiined by T, which is usually much longer than the phase memory time Ty that limits the observation of the two-pulse ESE. 

In an experiment, tcp is to be varied systematically to obtain the 2D data matrix. For the spin-echo and stimulated-echo based sequences, molecular diffusion causes signal decay in the first segment, thus both are called diffusion-editing sequences. 

The reference scan is to measure the decay due to spin-lattice relaxation. Compared with the corresponding stimulated echo sequence, the reference scan includes a jt pulse between the first two jt/2 pulses to refocus the dephasing due to the internal field and the second jt/2 pulse stores the magnetization at the point of echo formation. Following the diffusion period tD, the signal is read out with a final detection pulse. The phase cycling table for this sequence, including 2-step variation for the first three pulses, is shown in Table 3.7.2. The output from this pair of experiments are two sets of transients. A peak amplitude is extracted from each, and these two sets of amplitudes are analyzed as described below. 

Fig. 15. Effects of small-amplitude reorientation on 2H NMR stimulated-echo experiments, as calculated by means of RW simulations. The C-2H bonds perform rotational random jumps on the surface of a cone with a full opening angle % = 6°, which are governed by a broad logarithmic Gaussian distribution of correlation times G(lgr) (a = 2.3). (a) Correlation functions m tp — 30 is) for the indicated mean logarithmic time constants lgr 1. The calculated data are damped by an exponential decay, exp[—(tm/rso)] with rSD = 1 s, so as to mimic effects due to spin diffusion. The dotted lines are fits with Fcos(tm tp) = (1—C) expHtm/t/l + Qexp[—Om/rso)]- (b) Amplitude of the decays, 1-C,p, for various t resulting from these fits. The dotted line is the value of the integral in Eq. (12) as a function of rm. (Adapted from Ref. 76).

Fig. 6.25. Simulation of the effect of the diffusion time on the normalized signal decay for the two site exchange model as a function of the diffusion time (A) in a stimulated echo-based diffusion sequence. (Reproduced with permission from ref. [11c]. Copyright 2005 Wiley-VCH.)...

To bypass receiver deadtime effects, wideline spectra are derived by Fourier transformation of the decay of an echo. By use of the Hahn echo and the stimulated echo (Section 2.2.1), wideline spectra of and other spin-5 nuclei can be measured, for example, but not the spectra of dipolar coupled spins and of quadrupolar nuclei like H. The magnetization of nuclei with spin / = 1 can be refocused by the quadrupole echo or the solid echo, and by the Jeener-Broekaert echo or the alignment echo [Slil] (Fig. 3.2.6). 

Fig. 28. Signal decay plots from stimulated echo PEG experiments on PEO 1500 (M = 1500 g/mol) (a) and PEO 600 (M = 600 g/mol) (b) in a dispersion of block-copol)mier vesicles. The solid lines represent the best fit calculations based on the parameters kex and listed in Table 2, the assignments are given by symbols on the right margin.

Fig. 29. Signal decay plots from stimulated echo PFG experiments on PEO 400 =400 g/mol)...

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