Kinetic theory of bimolecular reactions in liquid. III. Reversible association–dissociation: A+B⇄C

Abstract

Articles you may be interested inWater-gas-shift reaction on metal nanoparticles and surfacesThe integral encounter theory of multistage reactions containing association-dissociation reaction stages. III. Taking account of quantum states of reactants A theoretical formalism based on the fully renormalized kinetic theory is applied to a diffusion-influenced pseudo-first order reaction kinetics of reversible association-dissociation A ϩB C including unimolecular decay processes. Linear response of the system, initially at equilibrium, to a thermal perturbation is examined and a rate kernel equation for the reactant concentrations is derived. The rate kernel has a hierarchical structure and the propagator appeared in the kernel expression is truncated by a disconnected approximation. When the unimolecular reactions are turned off, the response of the system not only shows the long-time power law of t Ϫ3/2 but also displays the proper behavior over the whole time region in accordance with previous computer simulation results. Moreover, it is shown that the amplitude of the long-time behavior predicted by previous workers is modified by a certain correction factor P which contains dynamical correlation effects. In this way, many-body complication inherent to the history of reactive pair creation is properly implemented in the description of the reversible kinetics. We compare the present theory with the other existing theories such as the rate equation, the superposition approximation, and the convolution approaches. In some limiting cases, results obtained from the present theory can be reduced to those from the existing theories.

Three-pulse photon echoes for model reactive systems

“…When the population transfer time scale is comparable to that of the degrees of freedom of the bath, the population transfer kinetics should be described by a rate kernel equation in which the rate kernel contains the information of the bath dynamics. [28][29][30][31] Understanding the dynamics of such systems is a topic of much current interest. 32 However, Markovian reactive systems in which the rate kernel is approximated by a time-independent rate constant provide a good starting point of our discussion and should give us an intuitive understanding of the influence of reactive events on the 3PEPS experiment.…”

Effect of an external field on the reversible reaction of a neutral particle and a charged particle in three dimensions. II. Excited-state reaction

“…However, the present results can be used to devise efficient Brownian dynamics for accurate numerical results. [42][43][44][45][46] When quantum mechanical effects are non-negligible, we can apply the quantum correction methods [47][48][49][50] to classical data from efficient Brownian dynamics simulations.…”

Influence of the force interaction on accumulation of macroscopic correlations in elementary reaction A + B → C

“…Different many-particle techniques were proposed in the literature [24][25][26] but we use the method most closely related to the Encounter Theory notions. Such a method based on the adaptation of non-stationary quantum scattering theory techniques and non-equilibrium statistical mechanics methods to chemically reacting systems now has become possible [27][28][29][30][31][32][33][34].…”