Numerically refined reaction conditions for stochastic simulation of nonelementary trimolecular reactions between...

We study a system of diffusing point particles in which any triplet of particles reacts and is removed from the system when the relative proximity of the constituent particles satisfies a predefined condition. Proximity-based reaction conditions of this kind are commonly used in particle-based simulations of chemical kinetics to mimic bimolecular reactions (those involving just two reactants) and have been extensively studied. The rate at which particles react within the system is determined by the reaction condition and particulate diffusion. In the bimolecular case, analytic relations exist between the reaction rate and the distance at which particles react allowing modellers to tune the rate of the reaction within their simulations by simply altering the reaction condition. However, generalizing proximity-based reaction conditions to trimolecular reactions (those involving three particles) is more complicated because it requires understanding the distribution of the closest diffusing particle to a point in the vicinity of a spatially dependent absorbing boundary condition. We find that in this case the evolution of the system is described by a nonlinear partial integrodifferential equation with no known analytic solution, which makes it difficult to relate the reaction rate to the reaction condition. To resolve this, we use singular perturbation theory to obtain a leading-order solution and show how to derive an approximate expression for the reaction rate. We then use finite-element methods to quantify the higher-order corrections to this solution and the reaction rate, which are difficult to obtain analytically. Leveraging the insights gathered from this analysis, we demonstrate how to correct for the errors that arise from adopting the approximate expression for the reaction rate, enabling for the construction of more accurate particle-based simulations than previously possible.