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T Insert: variation with laser intensity of transient optical density at 450 nm. benzene (Chantrell et al, 1977). 7 X 1 0 d m m o l ~ s ) . , 1980). This spectrum is similar to that obtained by pulse radiolysis but is extended to 9 3 1 _ 1 ence spectrum for the ground state absorption. The insert in Fig. 3b shows the plot of AOD against laser intensity. These data yielded a value for e of 35 000 d m m o l c m at 450 nm, again in good agreement with the value of 36 000 d m m o l c m quoted by Chantrell et al.

Also, the Ti So rate constants for the individual spin sublevels of the chlorophyll a dimer and monomer were reported; once again these individual values are very similar for the monomeric and dimeric species, indicating that the dimer is of a plane parallel structure in agreement with that proposed by Fong et al. (1977) and Boxer and Closs (1976). x confirmed by Gradyushko et al. 3). , 1973). 50 for Chl a and b respectively. These values are generally agreed to be too low. , 1949). These results can be at least partially understood in terms of the photodisaggregation of chlorophyll dimers following irradiation to give triplet and ground state monomeric species (Periasamy and Linschitz, 1979).

1 0 1 3 1 As noted above for chlorophylls, porphyrins were amongst the first biological molecules to be studied by flash photolysis. Thus Livingston and co-workers reported the triplet spectra for PP, in both methanol and pyridine (Livingston and Fujimori, 1958) and for CP dimethyl ester (CP DME) in benzene (Livingston, 1954). In a general way similar results to those discussed above for the chlorophylls were obtained. In each case there is a broad, relatively structureless absorption extending to the red but with a definite maximum lying to the long wavelength side of the Soret peak.

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An Advanced Treatise on Physical Chemistry. Volume Two: The Properties of Liquids. First Edition. by J R Partington


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