Simulating Enzyme Reactivity: Computational Methods in Enzyme Catalysis
Chapter 5: Kinetic Isotope Effects
Published:16 Nov 2016
Special Collection: 2016 ebook collection
I. H. Williams, P. B. Wilson, 2016. "Kinetic Isotope Effects", Simulating Enzyme Reactivity: Computational Methods in Enzyme Catalysis, Inaki Tunon, Vicent Moliner
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Methods for calculation of kinetic isotope effects and their application to reactions catalysed by enzymes are surveyed, including consideration of cut-off approximations both old and new, empirical bond-order–bond-energy approaches, quantum-mechanical cluster methods, and hybrid quantum mechanics/molecular mechanical methods. The unifying feature is the use of a Hessian matrix of force constants within the harmonic approximation. The merits of methods appropriate for supramolecular systems, including enzymes, are discussed in contrast to commonly used methods developed for gas-phase molecules, and the importance of averaging in conformationally flexible systems is emphasised.