Spectral echo pulse

Hydrochloride salts have been popular materials to study, particularly in recent years, as evidenced by the reports of Bryce et al., Chapman and Bryce, and Hamaed et al. (see Figure 11 for an example). Data are summarized in Table 4. To the best of our knowledge, the first chlorine SSNMR report for a powdered hydrochloride salt appears to be that of Pines and co-workers, who studied cocaine hydrochloride in 1995. The study utilized multiple techniques to study the hydrochloride salt, including N NQR. The chlorine-35 SSNMR experiment was carried out at 7.0 T using a Hahn-echo pulse sequence, and a chlorine-35 Cq of 5.027 MHz was reported. To avoid the intensity distortions that result from a finite pulse applied to a broad line shape, a variable frequency offset approach, in which the frequency was stepped in 2 or 4 kHz increments over the entire spectral width, was used to acquire the spectrum. 

Figure 8.2(c) is an inversion-recovery quadrupole echo pulse sequence, which is used to measure the Zeeman spin-lattice relaxation time,, with quadrupole echo detection [8,9,115]. Pre-saturation (Figure 8.2(d)) or progressive saturation (variation of the delay between transients) are also used to measure T. Notably, pre-saturation with spectral subtraction can separate the spectra of domains with different and is used to obtain the individual spectra of the amorphous and crystalline regions of semicrystalline polymers [8]. Also, Void and co-workers have recently presented methods involving selective inversion for the measurement of slow molecular reorientation, which provide an alternative to spin alignment or multidimensional methods [116]. 

The stated aim of this review is to demonstrate that elassical analyses of physieal organie ehemistry are feasible with respect to complex systems such as supported metal catalysts through the application of advanced EMR spectroscopic techniques and determining the relevant spin Hamiltonian parameters via the Zeeman-dependent hyperfine spectrum. The principles of analysis were outlined in the preceding section and entail replicate collection of ESEEM or ENDOR spectra by incremental steps and mapping the trajectory of peak positions. Deconvolution of peaks may be made either by traditional tau-suppression in the stimulated echo pulse sequence or via advanced pulse sequences such as HYSCORE (2-D ESEEM, Hofer, 1994). Mapping of spectral peak position as it varies depending on the Zeeman field is very important to the accurate determination of hyperfine terms. 

The common civil engineering seismic testing techniques work on the principles of ultrasonic through transmission (UPV), transient stress wave propagation and reflection (Impact Echo), Ultrasonic Pulse Echo (UPE) and Spectral Analysis of Surface Waves (SASW). 

In electron-spin-echo-detected EPR spectroscopy, spectral infomiation may, in principle, be obtained from a Fourier transfomiation of the second half of the echo shape, since it represents the FID of the refocused magnetizations, however, now recorded with much reduced deadtime problems. For the inhomogeneously broadened EPR lines considered here, however, the FID and therefore also the spin echo, show little structure. For this reason, the amplitude of tire echo is used as the main source of infomiation in ESE experiments. Recording the intensity of the two-pulse or tliree-pulse echo amplitude as a function of the external magnetic field defines electron-spm-echo- (ESE-)... 

In electron spin echo relaxation studies, the two-pulse echo amplitude, as a fiinction of tire pulse separation time T, gives a measure of the phase memory relaxation time from which can be extracted if Jj-effects are taken into consideration. Problems may arise from spectral diflfrision due to incomplete excitation of the EPR spectrum. In this case some of the transverse magnetization may leak into adjacent parts of the spectrum that have not been excited by the MW pulses. Spectral diflfrision effects can be suppressed by using the Carr-Purcell-Meiboom-Gill pulse sequence, which is also well known in NMR. The experiment involves using a sequence of n-pulses separated by 2r and can be denoted as [7i/2-(x-7i-T-echo) J. A series of echoes separated by lx is generated and the decay in their amplitudes is characterized by Ty. ... 

Figure Bl.15.16. Two-pulse ESE signal intensity of the chemically reduced ubiqumone-10 cofactor in photosynthetic bacterial reaction centres at 115 K. MW frequency is 95.1 GHz. One dimension is the magnetic field value Bq, the other dimension is the pulse separation x. The echo decay fiinction is anisotropic with respect to the spectral position.

In addition to sample rotation, a particular solid state NMR experiment is further characterized by the pulse sequence used. As in solution NMR, a multitude of such sequences exist for solids many exploit through-space dipolar couplings for either signal enhancement, spectral assignment, interauclear distance determination or full correlation of the spectra of different nuclei. The most commonly applied solid state NMR experiments are concerned with the measurement of spectra in which intensities relate to the numbers of spins in different environments and the resonance frequencies are dominated by isotropic chemical shifts, much like NMR spectra of solutions. Even so, there is considerable room for useful elaboration the observed signal may be obtained by direct excitation, cross polarization from other nuclei or other means, and irradiation may be applied during observation or in echo periods prior to... 

As evidenced from the above discussion, vibrational line shapes provide information mostly about intermolecular structure. Transient hole burning and more recently echo experiments, on the other hand, can provide information about the dynamics of spectral diffusion. The first echo experiments on the HOD/ D2O system involved two excitation pulses, and the signal was detected either by integrating the intensity [20] or by heterodyning [22]. The experiments were analyzed with the standard model assuming Gaussian frequency fluctuations. The data were consistent with a spectral diffusion TCF that was bi-exponential, involving fast and slow times of about 100 fs and 1 ps, respectively. 

Shortly thereafter came reports of integrated three-pulse photon echoes, especially using the echo peak shift to provide information about spectral diffusion [21, 23]. In one experiment [10, 23] the peak shift shows an intriguing oscillation at short times with a period of about 180 fs, followed by a slower relaxation with a decay time of 1.4 ps. The three-pulse echo amplitude can also be heterodyned, leading to 2DIR experiments [24 26]. The latter experiments provide a wealth of information, and there are several ways to extract the desired spectral diffusion dynamics [149]. 

Fig. 7. Double spin-echo imaging sequence for chemical shift selective imaging. The sequence applies spectral-spatial excitation pulses as presented in Fig. 6. Refocusing is performed with standard slice selective 180° pulses. For the examples in Fig. 8 echo times were chosen to TEi = 20 ms and TE2 = 60 ms.

---