Generalizations of the Fuoss approximation for ion pairing.

An elementary statistical observation identifies generalizations of the Fuoss approximation for the probability distribution function that describes ion clustering in electrolyte solutions. The simplest generalization, equivalent to a Poisson distribution model for inner-shell occupancy, exploits measurable interionic correlation functions, and is correct at the closest pair distances whether primitive electrolyte solutions models or molecularly detailed models are considered, and for low electrolyte concentrations in all cases. With detailed models, these generalizations include nonionic interactions and solvation effects. These generalizations are relevant for computational analysis of bimolecular reactive processes in solution. Comparisons with direct numerical simulation results show that the simplest generalization is accurate for a slightly supersaturated solution of tetraethylammonium tetrafluoroborate in propylene carbonate ([tea][BF(4)]/PC), and also for a primitive model associated with the [tea][BF(4)]/PC results. For [tea][BF(4)]/PC, the atomically detailed results identify solvent-separated nearest-neighbor ion-pairs. This generalization is examined also for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) where the simplest implementation is less accurate. In this more challenging situation an augmented maximum entropy procedure is satisfactory, and explains the more varied near-neighbor distributions observed in that case.