Fluctuations in the ensemble of reaction pathways

The dominant reaction pathway is a rigorous framework to microscopically compute the most probable trajectories, in nonequilibrium transitions. In the low-temperature regime, such dominant pathways encode the information about the reaction mechanism and can be used to estimate nonequilibrium averages of arbitrary observables. On the other hand, at sufficiently high temperatures, the stochastic fluctuations around the dominant paths become important and have to be taken into account. In this work, we develop a technique to systematically include the effects of such stochastic fluctuations, to order kBT. This method is used to compute the probability for a transition to take place through a specific reaction channel and to evaluate the reaction rate. © 2011 American Institute of Physics.