Theoretical Aspects of Proton Transfer Reactions in a Polar Environment

Theoretical Aspects of Proton Transfer Reactions in a Polar Environment 

Hydrogen-Transfer Reactions. Edited by J. T. Hynes, J. P. Klinman, H. H. limbach, and R. L. Schowen 

Copyright 2007 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim 

Further aspects of the standard W-M approach are most usefully discussed via its treatment of KIEs for the rate constant resulting from isotopic substitution -most often replacement of H with D - which is widely used in assessing the character of the TS and the proton s role therein. With the use of TS theory, the KIE arises from the exponentiated activation energies [8,12-14]. For H versus D transfer, the KIE is given by 

As is of course well-known, the KIEs originate, in this framework, from isotopic zero point energy (ZPE) differences between the reactant and the TS [8, 12-14, 

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