Paramagnetic relaxation removing

Aside from the question of the precise model by which relaxation times are interpreted there is the more practical problem of isolating that part of the relaxation specifically caused by diffusion. The contributions of exchange processes (see below), spin-rotation interaction (9), and spin diffusion (9) can be identified by temperature dependences different from that which is solely the result of the motionally modulated nuclear dipolar interaction as sketched above, and corrections can be made. The molecular rotation contributions to dipolar relaxation can be removed or corrected for by (a) isotopic substitution methods (19), (b) the fact that rotation is in some cases much faster than diffusion, and its relaxation effects are shifted to much lower temperatures (7, 20), and (c) doping with paramagnetic impurities as outlined above. The last method has been used in almost all cases reported thus far, more by default than by design, because commercial zeolites are thus doped by their method of preparation this... 

In the case of T measurements we have mentioned that cross relaxation provides multiexponential magnetization recovery (Sections 1.7.4 and 7.2.2). A far less known analogy may occur in the linewidths, as already discussed (Section 8.8) when two protons are dipole-dipole coupled and cross correlation occurs between Curie relaxation and proton-proton dipolar relaxation. In this case, we are in the presence of two overlapping signal components with different linewidths, i.e. of biexponentiality in T2 [35], Pulse sequences are available to remove the effects of cross correlation [36]. Such effects are common in paramagnetic metalloproteins where Curie relaxation is usually relevant (in principle, such cross correlation effects can be operative also in the case of 7i, although only to the extent that Curie relaxation on T is effective). 

The amount of radicals in carbon black filled rubbers decreases significantly upon extraction of free rubber with the aid of a solvent containing a free radical scavenger. The extraction nevertheless causes a substantial increase in the fraction of the T2 relaxation component with the decay time of about 0.02-0.03 ms [62], This increase is apparently caused by an increase in the total rubber-carbon black interfacial area per volume unit of the rubber due to the removal of free rubber. The T2 relaxation component with a short decay time is also observed in poly(dimethyl siloxane) (PDMS) filled with fumed silicas [88], whose particles contain a minor amount of paramagnetic impurities. Apparently, free radicals hardly influence the interpretation of NMR data obtained for carbon-black rubbers in any drastic way [62, 79]. 

Although most lanthanide ions are paramagnetic, because of rapid relaxation effects, spectra can be obtained only at low temperatures (often 4.2 K) in most cases. From the point of view of the chemist, EPR spectra are readily obtained (at room temperature) only from the f Gd +, with its 87/2 ground state. The sublevels of this state are degenerate in the absence of a crystal field (in a free Gd + ion), but are split into four Kramers doublets, with M/-values of 1/2, 3/2, 5/2 and 7/2. The application of a magnetic field removes the degeneracy of each doublet, and transitions can occur on irradiation with microwave radiation, subject to the usual selection rule of AM/ = 1. 

Observed linewidths of NMR signals in paramagnetic systems vary enormously and the conditions that govern the observed widths are considerably more complex than in diamagnetic systems. Swift (30) reviewed the problem some years ago. Relaxation times of spin-j nuclei are governed by dipolar and hyperfine exchange (Fermi contact) relaxation processes. The dipolar interaction is normally dominant except in some delocalized systems in which considerable unpaired spin density exists on nuclei far removed from the metal ions (e.g. Ti-radicals). Distinction between the two processes can be made by consideration of the different mathematical expressions involved. For dipolar relaxation when o)fx 1 (t = rate constant for rotation of the species containing the coupled pair and to, = nuclear resonance frequency) ... 

The width of the lines in solution spectra is increased if the life-time of an excited spin-state is reduced. This follows from the uncertainty principle an uncertainty in the life-time of a state is correlated with an uncertainty in the energy of that state so that, for a fixed frequency, resonance occurs over a wide range of values of the applied field. The relaxation time of an excited spin-state can be reduced by spin-lattice, spin-orbit, and spin-spin interactions it is usually necessary to remove extraneous paramagnetic species (e.g. oxygen) from the solution in order to reduce line-broadening by spin-spin interactions. 

Thus, in cases where long T s are expected from intrinsic relaxation mechanisms, care must be taken during sample preparation to remove as much of these impurities as possible. An especially common paramagnetic impurity in liquid as well as condensed gas samples is molecular oxygen. 

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