相关论文: Transition states and entangled mass action law
Recently, Gorban (2021) analysed some kinetic paradoxes of the transition state theory and proposed its revision that gave the "entangled mass action law", in which new reactions were generated as an addition to the reaction mechanism under…
In this paper we reconsider the Mass Action Law (MAL) for the anomalous reversible reaction $A\rightleftarrows B$ with diffusion. We provide a mesoscopic description of this reaction when the transitions between two states $A$ and $B$ are…
The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying theories of chemical kinetics, which are transition state theory, collision…
In its general definition, the law of mass action posits that, in systems where multiple elements move randomly, the rate by which they physically interact is proportional to the product of their densities. This law predicts the rate of…
The law of mass action is used widely. The law of mass action does not automatically conserve current, as is clear from mathematics of a simple case, chosen to illustrate the issues. The law of mass action does not force a series of…
Semiclassical instanton theory is a form of quantum transition-state theory which can be applied to computing thermal reaction rates for complex molecular systems including quantum tunneling effects. There have been a number of attempts to…
The transition states and dividing surfaces used to find rate constants for bimolecular reactions are shown to undergo qualitative changes, known as Morse bifurcations, and to exist for a large range of energies, not just immediately above…
Electron Transfer (ET) reactions are modeled by the dynamics of a quantum two-level system (representing the electronic state) coupled to a thermalized bath of classical harmonic oscillators (representing the nuclei degrees of freedom).…
Transition rates in continuously driven steady states were derived in [Evans R M L, 2005 J. Phys. A: Math. Gen. 38, 293] by demanding that no information other than the microscopic laws of motion and the macroscopic observables of the…
A model is proposed for studying the reaction dynamics in complex quantum systems in which the complete mixing of states is hindered by an internal barrier. Such systems are often treated by the transition-state theory, also known in…
When modelling driven steady states of matter, it is common practice either to choose transition rates arbitrarily, or to assume that the principle of detailed balance remains valid away from equilibrium. Neither of those practices is…
On example of diffusion-limited reversible $A+A \rightleftharpoons B$ reactions we re-examine two fundamental concepts of classical chemical kinetics - the notion of "Chemical Equilibrium" and the "Law of Mass Action". We consider a general…
Transition State Theory overestimates reaction rates in solution because conventional dividing surfaces between reagents and products are crossed many times by the same reactive trajectory. We describe a recipe for constructing a…
This work inspects the thermally activated transfer of solute particles across the interface between two interstitial solid solution phases that equilibrate internally by fast diffusion on conserved arrays of sites. When each phase is…
Entanglement can modify light-matter interaction effects and, conversely, these interactions can change the non-classical correlations present in the system. We present an example where these mutual connections can be discussed in a simple…
Just as transition rates in a canonical ensemble must respect the principle of detailed balance, constraints exist on transition rates in driven steady states. I derive those constraints, by maximum information-entropy inference, and apply…
We study chemical reactions with complex mechanisms under two assumptions: (i) intermediates are present in small amounts (this is the quasi-steady-state hypothesis or QSS) and (ii) they are in equilibrium relations with substrates (this is…
The standard transition state theory (TST) of bimolecular reactions was recently shown to lead to a rate law in disagreement with the expected second order rate law [Bonnet L., Rayez J.-C. Int. J. Quantum Chem. 2010, 110, 2355]. An…
Transition state theory (TST) is generalized for the nonequilibrium system with power-law distributions. The stochastic dynamics that gives rise to the power-law distributions for the reaction coordinate and momentum is modeled by the…
The quantum normal form approach to quantum transition state theory is used to compute the cumulative reaction probability for collinear exchange reactions. It is shown that for heavy atom systems like the nitrogen exchange reaction the…