Transition states and entangled mass action law
arXiv:2007.08225 · doi:10.1016/j.rinp.2021.103922
Abstract
The classical approaches to the derivation of the (generalized) Mass Action Law (MAL) assume that the intermediate transition state (i) has short life time and (ii) is in partial equilibrium with the initial reagents of the elementary reaction. The partial equilibrium assumption (ii) means that the reverse decomposition of the intermediates is much faster than its transition through other channels to the products. In this work we demonstrate how avoiding this partial equilibrium assumption modifies the reaction rates. This kinetic revision of transition state theory results in an effective `entanglement' of reaction rates, which become linear combinations of different MAL expressions.
arXiv commentSignificantly extended version with more explanation, illustrations, and references
References in corpus (8)
- Model reduction in chemical dynamics: slow invariant manifolds, singular perturbations, thermodynamic estimates, and analysis of reaction graph
- The Michaelis-Menten-Stueckelberg Theorem
- Jump Markov models and transition state theory: the Quasi-Stationary Distribution approach
- Timing of Transients: Quantifying Reaching Times and Transient Behavior in Complex Systems
- Detailed balance in micro- and macrokinetics and micro-distinguishability of macro-processes
- Non-uniqueness of quantum transition state theory and general dividing surfaces in the path integral space
- New universal Lyapunov functions for non-linear reaction networks
- Singularities of transient processes in dynamics and beyond