| Transition State Theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when the reactive system is coupled to an environment. The calculations made in this way then overestimate the reaction rate and the results depend critically on the choice of the dividing surface. I will describe the phase space of a stochastically driven system close to an energetic barrier in order to identify the geometric structures that unambiguously determines the reactive trajectories. They can be incorporated in a simple rate formula for reactions in condensed phase that is both independent of the dividing surface and exact. |
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