Journal
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
Volume 1458, Issue 1, Pages 6-27Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/S0005-2728(00)00057-8
Keywords
adiabatic process; nonadiabatic process; activation energy; tunneling probability; kinetic isotope effect
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A brief summary of the principal notions of the quantum-mechanical theory of the charge transfer reactions has been presented. In the framework of this theory, the mechanism of the proton transfer consists in the classical medium reorganization that equalizes the proton energy levels in the initial and final states, and a consequent proton transfer via a quantum-mechanical underbarrier transition. On the basis of this mechanism, factors influencing the proton transfer probability, and hence kinetic isotope effect, have been discussed; among them are the optimum tunneling distance, the involvement of the excited vibrational states, etc. Semi-classical and quantum-mechanical treatments of the Swain-Schaad relations have been compared. Some applications to enzymatic proton-transfer reactions have been described. (C) 2000 Elsevier Science B.V. All rights reserved.
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