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 desktop expertise have strongly inspired study at the dynamic behaviour of excited states and different transients. This quantity displays the numerous advances in experimentation and interpretation within the box, offering new insights into the heritage of molecules that soak up radiation. it truly is a part of a continual sequence meant to discover the frontiers of photochemistry.

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These conclusions are not entirely satisfactory, because though 713%which is determined by the dynamics of y-Habstraction, may show a small solvent dependence, it is unlikely that ken should be that sensitive to subtle solvent changes. 52 x 10" s-l are remarkably close to those obtained in Ref. 171 (see Table 12) and are consistent with the original conclusions. Experimental estimates of ken 3 9 x 10" s-' and ken 2 10" s-' TABLE 12. 85 "From Ref. 171. bMolar volumes at 20°C. , Sandusky, Ohio, 1956.

FAcetophenone-sensitized. gXanthone-sensitized. *Pulse radiolysis. 00for acridine. '2,s-di-t-Butylfuran. 'In n-hexane. 'From data for three [O,] values. "Neat ketone solvent; acetone, 2-butanone, 2-hexanone, 3-heptanone, and 4-heptanone all gave similar +A's (within a factor of 3) in methanol using DMF as probe (108). "Neglecting OZ(lAg)quenching by benzophenone (97). in oxygen-saturated solution is not included because it predicts too low T', "A higher value for for benzophenone (104,109). PCyclohexane.

Flash kinetic spectroscopy has been used to determine rate constants for triplet energy transfer from indeno[2,l-a]indene to azulene as a function of temperature in n-pentane (228-290 K), toluene (228-309 K), acetonitrile (233-308 K), and r-butyl alcohol (309-342 K)(54). The adherenceof kobsd to the Arrheniusequation is satisfactory in all four solvents (Figure 15), and activation energies for excitation transfer are close to those for r-butyl radical self-reaction and to activation energies for viscous flow (Table 13).

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