Home Physical Theoretical • Advances in Photochemistry (Volume 14) by David H. Volman, George S. Hammond, Klaus Gollnick

Advances in Photochemistry (Volume 14) by David H. Volman, George S. Hammond, Klaus Gollnick

By David H. Volman, George S. Hammond, Klaus Gollnick

Some time past 25 years, the emergence of lasers and machine know-how have strongly stimulated examine at the dynamic behaviour of excited states and different transients. This quantity displays the numerous advances in experimentation and interpretation within the box, providing new insights into the background of molecules that take up radiation. it's a part of a continuous sequence meant to discover the frontiers of photochemistry.

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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.

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