Fluctuations in the ensemble of reaction pathways

Area of Science:

• Statistical Mechanics
• Chemical Kinetics
• Computational Chemistry

Background:

• The dominant reaction pathway framework microscopically computes probable trajectories in nonequilibrium transitions.
• At low temperatures, these pathways reveal reaction mechanisms and allow estimation of nonequilibrium averages.
• At high temperatures, stochastic fluctuations around dominant paths become significant and require consideration.

Purpose of the Study:

• To develop a systematic technique for including stochastic fluctuation effects up to order k(B)T.
• To enhance the accuracy of calculating transition probabilities through specific reaction channels.
• To improve the evaluation of reaction rates in nonequilibrium systems.

Main Methods:

• Developing a theoretical framework to incorporate stochastic fluctuations.
• Systematically including effects of fluctuations to order k(B)T.
• Applying the method to compute transition probabilities and reaction rates.

Main Results:

• A novel technique to systematically include stochastic fluctuations in dominant reaction pathway calculations.
• The method accounts for the impact of fluctuations at higher temperatures.
• Accurate computation of transition probabilities and reaction rates is enabled.

Conclusions:

• The developed technique provides a more accurate description of reaction dynamics in nonequilibrium systems.
• This method enhances the predictive power of the dominant reaction pathway framework.
• It offers a way to precisely calculate reaction rates and probabilities by including thermal fluctuations.