By Gerald Oster and Arthur W. Pollister (Eds.)

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In other words, as a result of the chemical rearrangement of the participating substances some molecule is left in an excited state, and this molecule returns to its ground state in a secondary process by radiating the energy of excitation as light of the appropriate wave length. If the excited state is the same state which the normal molecule reaches by absorbing light, then the chemiluminescence spectrum is identical with the fluorescence spectrum. Since the ability of an excited molecule to emit light is independent of the method by which the excitation occurred, chemiluminescent substances must invariably be molecules that are able to fluoresce.

P H dependence of the quantum yield for inactivation of proteins has been another type of photochemical observation that has been correlated with structure. Many proteins show a minimum value of the yield near the iso-electric point (McLaren, 1949). The interpretation has been advanced that since the protein is most compact at the iso-electric point, the recombination of radicals by the caging effect would be greatest. On either side of the iso-electric point the molecule will be stretched out because of repulsion of like charges; hence, radicals formed by a primary PHOTOCHEMISTRY AND LUMINESCENCE 25 light process will have a greater chance of escaping from each other before recombination could occur.

The reaction of one molecule of carbon dioxide with water to give one molecule of oxygen plus carbohydrate is an endothermic reaction requiring more energy than is contained in a single quantum of light absorbed by chlorophyll. On a molar basis, about 115 kcal is needed for the reaction and the amount available in light of 7000 A , the longest wave length which chlorophyll can utilize efficiently, is only 41 kcal per einstein or 4 from Eq. (2). Thus, the maximum quantum yield would be H i 5 -36 if all of the light energy were converted completely into the chemical energy for the overall reaction.

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