The Quantum Theory of the Kinetics of Homogeneous and Heterogeneous Reactions

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CLASSICAL physical chemistry cannot explain a whole number of questions connected with the kinetics of homogeneous and heterogeneous reactions. For the explanation in particular of unimolecular reactions the constant of velocity of which does not depend on pressure, it is necessary to postulate a more or less complex mechanism (Lindemann, Lewis and Perrin, etc.). A number of investigators (Oppenheimer, Bourgin) have recently pointed out that, from the point of view of quantum mechanics, spontaneous disintegration of molecules which had not received the activation energy required by the classical theory is possible. In the present communication we give some preliminary considerations resulting from a study of the problem of kinetics of reactions.1

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  1. 1

    After this communication had been posted, there was pointed out to us the preliminary paper of Langer (Phys. Rev., 37, 92; 1929) devoted to the quantum mechanics of chemical reactions. This communication (and especially our further investigations) seems to us to have an interest of its own, since we put the question (and solve it) in a way which differs in many respects from Langer's . (Added in proof.)

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