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Extra resources for Advances in Photochemistry (Volume 14)
11 (s25%), its use with higher-molecular-weight solvents and solutes is not recommended. Finally, when diffusion-controlled 2kt values are available in a specific solvent for radicals with D close to that for an A + B reaction, kdif for that reaction can be taken as 8k. * VI. TRIPLET EXCITATION TRANSFER Triplet excitation transfer involves a multiplicity-allowed electron exchange interaction in an encounter pair (178). - 55 TRIPLET EXCITATION TRANSFER 3D* + 'A e kdd k-d# '(D*A) ken k-cn 3(DA*) k-dd 'D + 3A* (64) When, based on spectroscopic triplet excitation energies, the process is at least 3 kcal/mol exothermic, it has been found to attain a maximum rate constant (1, 5, 179-181) and has often been considered to occur upon every solution encounter.
Since p is insensitive to temperature in all solvents employed, it appears that the activation energies of ken and k-dif must be similar. A more quantitative demonstration of this fact can be based on a comparison of rate constants for benzyl radical termination with rate constants for In-Az triplet excitation transfer in toluene (Table 14). Values of p in Table 14, based on the assumption that kdif = 8kt, are probably underestimated by - TABLE 14. 12 "Based on Arrhenius parameters from data in Ref.
TABLE 13. 4 Source: Table VEI in Ref. 54; A,, in poise, AoM in M-' s-', E's in kcal/mol. 2, respectively. Figure 16. Plots of kObd for 31n*-'Az energy transfer vs. k, for t-butyl radicals; lines 1-4 are for t-butyl alcohol, n-pentaneln-heptane, toluenehnzene, and acetonitrile, respectively. The dashed line is drawn with 0 intercept and slope 4. From Ref. 54, reprinted with permission from J . Am. Chern. Soc. (1980), 102,6799. Copyright 1980, American Chemical Society. 58 TRIPLET EXCITATION TRANSFER 59 where t-Bu, Az, and In designate the solutes.