Couplings, short relaxation times effects

The 13C NMR sensitivity can sometimes be a problem, but for the kind of samples studied here the effective concentration of monomer units is several molar which does not place excessive demands on present Fourier transform NMR spectrometers. In addition to the sensitivity of the chemical shift to structure (9), the relaxation of protonated carbons is dominated by dipole-dipole interaction with the attached proton (9). The dependence of the relaxation parameters T, or spin-lattice, and Tor spin-spin, on isotropic motional correlation time for a C-H unit is shown schematically in Figure 1. The T1 can be determined by standard pulse techniques (9), while the linewidth at half-height is often related to the T2. Another parameter which is related to the correlation time is the nuclear Overhauser enhancement factor, q. The value of this factor for 13C coupled to protons, varies from about 2 at short correlation times to 0.1 at long correlation... 

For irradiation times of J short with respect to the relaxation time of / the NOE extent is independent of the relaxation time of the nucleus and provides a direct measurement of time required to saturate signal J is not negligible compared with t, the response of the system is not linear [18]. The truncated NOE is independent of paramagnetism as it does not depend on p/, which contains the electron spin vector S in the R[m term, and only depends on gkj), which does not contain S. If then the steady state NOE is reached, the value of p/ can also be obtained. This is the correct way to measure p/ of a nucleus, provided saturation of J can be considered instantaneous. In general, measurements at short t values minimize spin diffusion effects. In fact, in the presence of short saturation times, the transfer of saturation affects mainly the nuclei directly coupled to the one whose signal is saturated. Secondary NOEs have no time to build substantially. As already said, this is more true in paramagnetic systems, the larger the R[m contribution to p/. 

Short T, values and the absence of any NOE produces an absorption spectrum similar to that obtained for and with the same relative ease. The result is that much more chemical shift information has been gathered (3-6) in addition to a substantial amount of data concerning Si relaxation times, coupling constants, and Overhauser effects. 

So far, the spins have been considered as isolated entities, which are completely decoupled from the surrounding environment. This is, in fact a good approximation for short evolution times. For longer times, the coupling to the lattice must be considered. This can be done either by including the lattice in the density matrix or by introducing a relaxation operator T which summarily accounts for the effects of the lattice on each... 

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