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Bifurcations on Potential Energy Surfaces of Organic Reactions
Author(s) -
Ess Daniel H.,
Wheeler Steven E.,
Iafe Robert G.,
Xu Lai,
ÇelebiÖlçüm Nihan,
Houk Kendall N.
Publication year - 2008
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200800918
Subject(s) - transition state , chemistry , potential energy surface , kinetic energy , observable , potential energy , kinetic isotope effect , selectivity , chemical physics , bifurcation , energetics , transition state theory , thermodynamics , computational chemistry , kinetics , physics , atomic physics , molecule , organic chemistry , nonlinear system , catalysis , reaction rate constant , classical mechanics , quantum mechanics , deuterium
A single transition state may lead to multiple intermediates or products if there is a post‐transition‐state reaction pathway bifurcation. These bifurcations arise when there are sequential transition states with no intervening energy minimum. For such systems, the shape of the potential energy surface and dynamic effects, rather than transition‐state energetics, control selectivity. This Minireview covers recent investigations of organic reactions exhibiting reaction pathway bifurcations. Such phenomena are surprisingly general and affect experimental observables such as kinetic isotope effects and product distributions.