Binding reactions at finite systems

Abstract

A perpetual yearn exists among computational scientists to scale down the size of physical systems, a desire shared as well with experimentalists able to track single molecules. A question then arises whether averages observed at small systems are the same as those observed at large or macroscopic systems. Utilizing statistical-mechanics formulations in ensembles in which the total numbers of particles are fixed, we demonstrate that properties of binding reactions are not homogeneous functions. This means that averages of intensive parameters, such as the concentration of the bound-state, at finite systems are different than those at large systems. The discrepancy increases with decreasing temperature, volume, and to some extent, numbers of particles. As perplexing as it may sound, despite variations in average quantities, extracting the equilibrium constant from systems of different sizes does yield the same value. The reason is that correlations in reactants' concentrations ought to be accounted for in the expression of the equilibrium constant, being negligible at large-scale but significant at small-scale. Similar arguments pertain to the calculations of the reaction rate constants, more specifically, the bimolecular rate of the forward reaction is related to the average of the product (and not to the product of the averages) of the reactants' concentrations. Furthermore, we derive relations aiming to predict the composition only from the equilibrium constant and the system's size. All predictions are validated by Monte-Carlo and molecular dynamics simulations. An important consequence of these findings is that the expression of the equilibrium constant at finite systems is not dictated solely by the chemical equation of the reaction but requires knowledge of the elementary processes involved.