Beyond standard Poisson–Boltzmann theory: ion-specific interactions in aqueous solutions

The Poisson–Boltzmann mean-field description of ionic solutions has been successfully used in predicting charge distributions and interactions between charged macromolecules. While the electrostatic model of charged fluids, on which the Poisson–Boltzmann description rests, and its statistical mechanical consequences have been scrutinized in great detail, much less is understood about its probable shortcomings when dealing with various aspects of real physical, chemical and biological systems. These shortcomings are not only a consequence of the limitations of the mean-field approximation per se , but perhaps are primarily due to the fact that the purely Coulombic model Hamiltonian does not take into account various additional interactions that are not electrostatic in their origin. We explore several possible non-electrostatic contributions to the free energy of ions in confined aqueous solutions and investigate their ramifications and consequences on ionic profiles and interactions between charged surfaces and macromolecules.