By David H. Volman, George S. Hammond, Klaus Gollnick
Long ago 25 years, the emergence of lasers and laptop 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, featuring new insights into the background of molecules that soak up radiation. it really is a part of a continual sequence meant to discover the frontiers of photochemistry.
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Extra resources for Advances in Photochemistry (Volume 14)
Generally, rather small aT values are obtained for carbonyl compounds with n,n* lowest triplet states (Table 6) consistent with the large k;f; values associated with the quenching process. , benzophenone and benzaldehyde) despite the large triplet excitation energies involved, some interconversion of triplet and singlet encounter complexes, as shown in Eq. 37, is implied. The large fractions of quenching events which do not give OZ('Ag) (see especially the aliphatic ketones) have been attributed to charge-transfer quenching via the triplet encounter pair (52).
56 TRIPLET EXCITATION TRANSFER 57 have been based on the quenching of y-phenylbutyrophenone triplets by neat cis-l,3-pentadiene (17 1) and on transient measurements of benzophenone triplet decay in neat 1,3-pentadienes (184). 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).
These two methods modify the Stokes-Einstein relationship for DA (see Eqs. 10-14) by accounting for (1) the molecular sizes of solute and solvent and (2) the effects of different solute-solvent and solventsolvent interactions (6). A comparison of the experimental 2kt’s with theoretical 2kp’s based on Eqs. 6 A and the “best” calculated D ( = 2DA) is given in Fig. 9 (6). The points cluster about a line with slope one, as expected for the mechanism shown in Eq. 60. The same conclusion can be reached by plotting the experimental termination rate constants, 2kt, against the calculated diffusion coefficientsD,.
Advances in Photochemistry (Volume 14) by David H. Volman, George S. Hammond, Klaus Gollnick