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Chapter 5

Kinetic Isotope Effects

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.

Print publication date: 25 Nov 2016
Copyright year: 2017
Print ISBN: 978-1-78262-429-5
PDF eISBN: 978-1-78262-683-1
ePub eISBN: 978-1-78262-967-2