Fluctuations in the Ensemble of Reaction Pathways

Abstract

The dominant reaction pathway (DRP) is a rigorous framework to microscopically compute the most probable trajectories, in non-equilibrium transitions. In the low-temperature regime, such dominant pathways encode the information about the reaction mechanism and can be used to estimate non-equilibrium 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 k_B T. 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.

References in corpus (4)

• Quantitative Protein Dynamics from Dominant Folding Pathways
• Dominant Reaction Pathways in High Dimensional Systems
• Molecular Dynamics at Low Time Resolution
• Polymer Escape from a Metastable Kramers potential: Path Integral Hyperdynamics Study

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• Folding Pathways of a Knotted Protein with a Realistic Atomistic Force Field