By Ilya Prigogine, Stuart A. Rice
The Advances in Chemical Physics sequence offers the chemical physics and actual chemistry fields with a discussion board for serious, authoritative reviews of advances in each sector of the self-discipline. jam-packed with state of the art study mentioned in a cohesive demeanour no longer chanced on in other places within the literature, each one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complicated graduate category dedicated to the learn of chemical physics.
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Additional resources for Advances in Chemical Physics, Volume 1
21) 2 The problem of the transmission coefficient presents difficulty. One finds with model potential energy surfaces that transmission coefficients may depend strongly on the mass of the activated complex and its energy. 36 Further studv is required here. 22) the tunneling factor becomes to the first quantum approximation where If is the “effective mass” of the motion and Z L ~ * has been associated with the motion along the decomposition path. 24) In the case of symmetric exchange reactions one must consider transmission coefficients as shown in Section VI, if there exists a potential basin in the potential surface between two equivalent activated complex sites.
Under these conditions one must take into consideration all three species A’BA’,A‘BA, and ABd and the products X,Y ,X‘, and Y’ formed from each of them. The distribution of A and A’ between these species is not necessarily given by classical statistics. 52) where N , is the atom fraction of A . If the concentrations are expressed in mole fractions 47 ISOTOPE EFFECTS I N CHEMICAL KINETICS A ’ B A , and A B A According to Eqs. 57. 53) Solution of Eqs. 56) Apart from the molecular species H , or systems at very low temperatures, the values of 6 for all chemical species is of the order of lo-, or less6 Thus the correction for nonclassical equilibrium distribution to any species is at most one per cent.
In the simple unimolecular bond break, it does appear reasonable that the coordinate q between the two atoms A and B must reach and go beyond a critical extension yo in order that decomposition takes place. In Slater's calculations account is taken of the different energies involved in stretching q to qo. I n regarding q as the mode of decomposition in the transition state method, one must, however, first look at the potential energy surface. The decomposition path involves passage over the lojvest possible barrier between reactants and products.