By Wendell Forst
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Extra info for Theory of Unimolecular Reactions
Sample text
As a result of the crossing, ground state of products is a triplet, and hence dissociation of ground-state reactant to yield ground-state products involves a switchover from singlet to triplet potential energy surface. The essential point is that the multiplicities of the reactant and product(s) are different. Hence similar curve crossing is involved when reactant is decomposing from an excited state, as in photoactivation (Chapter 9, Section 6), to yield products in some other electronic state.
8). 40 3. Potential Energy Surfaces in Unimolecular Reactions separated by an energy col or saddle point. The progress of reaction can be conveniently followed by means of a progress variable, or reaction coordinate, suitably defined with respect to these topological features of the potential energy surface. For instance, if we assume that the reaction path follows the valley separating reactants and products in the direction of minimum curvature, the reaction coordinate may be defined as the distance along this path.
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