One hundred years of electrified interfaces: What’s new with the theories of Debye and Onsager?

The Poisson-Boltzmann theory stems from the pioneering works of Debye and Onsager and is considered even today as the benchmark of ionic solutions and electrified interfaces. It has been instrumental during the last century in predicting charge distributions and interactions between charged surfaces, membranes, electrodes as well as macromolecules and colloids. 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, however, is understood about its probable shortcomings when dealing with various aspects of real physical, chemical, and biological systems. After reviewing the Poisson-Boltzmann theory, I will discuss several extensions and modifications to the seminal works of Debye and Onsager as applied to ions and macromolecules in confined geometries. These novel ideas include the effect of dipolar solvent molecules, finite size of ions, ionic specificity, surface tension, and conductivity of concentrated ionic solutions.