Substrate concentration dependence of the diffusion-controlled steady-state rate constant

TL;DR

This paper extends the Smoluchowski theory to account for interactions among substrate particles, deriving an analytic expression for the steady-state rate constant at low concentrations, validated by simulations, and proposing a new experimental method for measuring virial coefficients.

Contribution

It generalizes the diffusion-controlled reaction theory to include interactions via osmotic pressure and hydrodynamics, providing an analytic formula for the rate constant.

Findings

Excellent agreement with simulations up to certain densities.

Provides a new experimental approach to measure virial coefficients.

Derives an analytic expression for the rate constant at low substrate concentrations.

Abstract

The Smoluchowski approach to diffusion-controlled reactions is generalized to interacting substrate particles by including the osmotic pressure and hydrodynamic interactions of the nonideal particles in the Smoluchoswki equation within a local-density approximation. By solving the strictly linearized equation for the time-independent case with absorbing boundary conditions, we present an analytic expression for the diffusion-limited steady-state rate constant for small substrate concentrations in terms of an effective second virial coefficient B_2*. Comparisons to Brownian dynamics simulations excluding HI show excellent agreement up to bulk number densities of B_2* rho_0 < 0.4 for hard sphere and repulsive Yukawa-like interactions between the substrates. Our study provides an alternative way to determine the second virial coefficient of interacting macromolecules experimentally by measuring their steady-state rate constant in diffusion-controlled reactions at low densities.