| Abstract
| - The classical reaction path Hamiltonian formulation of Miller, Handy, and Adams is reformulated using alinear expansion of the gradient in internal coordinates. It leads to a correspondence between the arc length,s, along the intrinsic reaction coordinate, and the whole set of internal coordinates and, furthermore, to adynamical equation for s, a second-order Bernoulli-type equation, which is analytically solvable inside thevalidity range of the quadratic expansion of the potential. Therefore, by virtue of the above correspondence,the time dependence of the whole set of internal coordinates is easily recovered, by means of a few functionaland overlap evaluations. It thus enhances the computational performance of the overall direct dynamics method.The unimolecular 1,2 hydrogen migration, between the (corresponding) carbene and ethyne oxide, is consideredas example for illustrative purposes.
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