Advances in Chemical Physics, Vol. 117 by Ilya Prigogine, Stuart A. Rice

By Ilya Prigogine, Stuart A. Rice

Delivering the chemical physics box with a discussion board for serious, authoritative reviews in each zone of the self-discipline, the newest quantity of Advances in Chemical Physics maintains to supply major, up to date chapters written via across the world well-known researchers.

This quantity is largely dedicated to aiding the reader receive basic information regarding a wide selection of issues in chemical physics. Advances in Chemical Physics, quantity 117 comprises chapters addressing laser photoelectron spectroscopy, nonadiabatic transitions because of curve crossings, multidimensional raman spectroscopy, birefringence and dielectric leisure in powerful electrical fields, and crossover formulae for Kramers conception of thermally activated get away rates.

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The reaction studied thus has both an intermolecular and an intramolecular isotope effect. Up to the approximation of no secondaryisotope effects, the high-pressure rate of isomerization of a protium atom in the labeled molecule will not differ significantly from that of the unlabeled molecule. 9at 775’K. The absoluteerrorof themeasurementisnaturally magnified by the statistical correction for the intramolecular dilution. Because of this intramolecular dilution, a reliable temperature coefficient of the ratio of rate constants cannot be obtained by a least square treatment of the experimental data.

51, the distribution of -4 and A ' , again excluding the isotopes of hydrogen, among the species A'B*i', A ' B A , and A B A will not be sufficiently skewed to affect the distributions given in Table 111. ( 7 ) The Determination of the Isotope Ratios and the Problem of Isotopic Homogeizeity Two methods of measurement of isotope ratios have been developed to a sufficient degree of accuracy to make them useful for the determination of isotope effects on reaction rates. They are measurements of radioactivity and mass spectrometry.

6) The quantity /,* will be evaluated for two models, a linear state ISOTOPE EFFECTS I N CHEMICAL KINETICS 55 and an isosceles triangular state. In the present calculations we utilize a prediction of Wheeler, Topley, and Eyring6* that the ratio of the H-H to the H-CI force constants in the transition state is a small negative number (about 10-I). 0 35 45 1031~ Fig. 4, Relative rates of reaction of the isotopic hydrogen molecules with chlorine atoms as a function of temperature. Solid lines calculated from the Wheeler, Topley, and Eyring potential for H,C1.

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