Radical pair theory polarization effects

With the establishment of the primary phototriplet reduction mechanism we now turn to the explanation for the effect of flow rates and the formation of polarized phenoxy radicals. Since reaction [2] is a relatively fast secondary process it is readily understood that the observation of the primary ketyl radicals will be dependent upon flow rate. The triplet polarization (E) of the secondary phenacyl radical should not have been affected but the increased contribution of the E/A Radical-Pair polarization altered the overall appearance of the polarization pattern. The diffusion model of the Radical-Pair theory relates the E/A polarization magnitude to the radical concentration within the reaction zone. Since the phenacyl radical is considered to be very chemically reactive, and the product phenol "accumulated" within the reaction zone is also a much better hydrogen donor, the following reactions will proceed within the reaction zone ... 

The first discovery of chemically induced dynamic electron polarization (CIDEP) was made by Fessenden and Schuler in 1963 (58). These authors observed the abnormal spectra of the H atoms produced during the irradiation of liquid methane. The low-field line in the esr spectrum was inverted compared to the corresponding high-field line. The related chemically induced dynamic nuclear polarization effect (CIDNP) was reported independently four years later by Bargon et al. (22) and by Ward and Lawler (134). Because of the wider application of nmr in chemistry, the CIDNP effect immediately attracted considerable theoretical and experimental attention, and an elegant theory based on a radical-pair model (RPM) was advanced to explain the effect. The remarkable development of the radical-pair theory has obviously brought cross-fertilization to the then-lesser-known CIDEP phenomenon. 

The current theories of chemically induced magnetic polarization can therefore be summarized into the two basically different mechanisms the photoexcited triplet mechanism (PTM) responsible for the initial electron polarization and the observed Overhauser effect in nuclear polarization, and the radical-pair mechanism which, to date, accounts for almost the remaining bulk of the known polarization systems. We proceed to describe the simple physical models of these two mechanisms by beginning with the more sophisticated radical-pair theory. 

Closs G L and Trifunac A D 1970 Theory of chemically Induced nuclear spin polarization. III. Effect of Isotropic g shifts In the components of radical pairs with one hyperfine Interaction J. Am. Chem. Soc. 92 2183-4... 

If a chemical reaction proceeds via two (or more) successive radical pairs, new aspects arise. The theory of this so-called pair substitution, also called momory effect or cooperative effect, has been developed by den Hollander [41]. In such a system the polarizations are not simply superpositions of polarizations from the first and second pair. Rather, they can be described as arising in a hypothetical radical pair with the combined magnetic properties of both pairs weighted with their respective lifetimes. Examples have even been reported [41b] where neither pair on its own would give rise to a net effect, one because of vanishing Ag and the other because of negligible a, but in combination they do. 

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