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- W2000149761 abstract "Calculations of the temperature dependent factor (TDF) in the isotopic ratio of specific rate constants kC12/kC13 for the decomposition of formic acid were carried out exactly and in the first order and second order high temperature approximations for a variety of reaction coordinate eigenvectors comprising displacements in three internal coordinates. The principal objective was to determine the consistency, if any, with which the features and general value levels of surfaces obtained by plotting exact values of ln(TDF) as functions of RCEV composition could be predicted from the corresponding surfaces in the first and second order approximations. The first order approximation is not usually a reliable guide to ln(TDF) for either value or gradients of value as functions of reaction coordinate composition at temperatures ? 1000°K. The second order approximation is often a reliable guide to gradients in the value of ln(TDF) in the range 1000−300°K, but the indications of value may be crude." @default.
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- W2000149761 title "Calculation of heavy‐atom kinetic isotope effects: Application of the high temperature approximation to models with three‐element reaction coordinates" @default.
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