Convex Arrhenius plots and their interpretation

Donald G. Truhlar, Amnon Kohen

Research output: Contribution to journalArticlepeer-review

111 Scopus citations

Abstract

This paper draws attention to selected experiments on enzyme-catalyzed reactions that show convex Arrhenius plots, which are very rare, and points out that Tolman's interpretation of the activation energy places a fundamental model-independent constraint on any detailed explanation of these reactions. The analysis presented here shows that in such systems, the rate coefficient as a function of energy is not just increasing more slowly than expected, it is actually decreasing. This interpretation of the data provides a constraint on proposed microscopic models, i.e., it requires that any successful model of a reaction with a convex Arrhenius plot should be consistent with the microcanonical rate coefficient being a decreasing function of energy. The implications and limitations of this analysis to interpreting enzyme mechanisms are discussed. This model-independent conclusion has broad applicability to all fields of kinetics, and we also draw attention to an analogy with diffusion in metastable fluids and glasses.

Original languageEnglish (US)
Pages (from-to)848-851
Number of pages4
JournalProceedings of the National Academy of Sciences of the United States of America
Volume98
Issue number3
DOIs
StatePublished - Jan 30 2001

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