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We present the theory and implementation of a Poisson-Boltzmann implicitsolvation model for electrolyte solutions. This model can be combined witharbitrary electronic structure methods that provide an accurate charge densityof the solute. A hierarchy of approximations for this model includes a linearapproximation for weak electrostatic potentials, finite size of the mobileelectrolyte ions and a Stern-layer correction. Recasting the Poisson-Boltzmannequations into Euler-Lagrange equations then significantly simplifies thederivation of the free energy of solvation for these approximate models. Theparameters of the model are then either fit directly to experimentalobservables, e.g. the finite ion size, or optimized for agreement withexperimental results. Experimental data for this optimization is available inthe form of Sechenov coefficients that describe the linear dependence of thesalting-out effect of solutes with respect to the electrolyte concentration. Inthe final part we rationalize the qualitative disagreement of the finite ionsize modification to the Poisson-Boltzmann model with experimental observationsby taking into account the electrolyte concentration dependence of the Sternlayer. A route towards a revised model that captures the experimentalobservations while including the finite ion size effects is then outlined. Thisimplementation paves the way for the study of electrochemical andelectrocatalytic processes of molecules and cluster models with accurateelectronic structure methods.

journal of chemical physics online/the journal of chemical physics/journal of chemical physics

The Poisson-Boltzmann model for implicit solvation of electrolyte  solutions: Quantum chemical implementation and assessment via Sechenov  coefficients