A New Look at the Transition State: Wigner's Dynamical Perspective Revisited

Department of Physics, Nagoya University, Nagoya, 464-8602, Japan
Advances in Chemical Physics (Impact Factor: 2.12). 01/2005; 130:171 - 216. DOI: 10.1002/0471712531.ch3

ABSTRACT In this article we review our general formulation of the nonlinear dynamics and geometry of classical reaction dynamics. Our formalism hinges on finding, for the first time, the dynamically exact higher dimensional structures (separatrices, dividing surfaces) which regulate transport between qualitatively different states (“reactants” and “products”) in three or more degrees of freedom. The work explained in this article has been a long-standing and often-expressed aspiration of the science and mathematics communities, but it is only now that we have the theoretical and computational tools for its fulfillment. We illustrate the theory on the isomerization of HCN.