The primitive model in classical density functional theory: beyond the standard mean-field approximation.

The primitive model describes ions by point charges with an additional hard-core interaction. In classical density-functional theory (DFT) the mean-field electrostatic contribution can be obtained from the first order of a functional perturbation of the pair potential for an uncharged reference system of hard spheres. This mean-field electrostatic term particularly contributes at particle separations that are forbidden due to hard-core overlap. In this work we modify the mean-field contribution such that the pair potential is constant for distances smaller than the contact distance of the ions. We motivate our modification by the underlying splitting of the potential, which is similar to the splitting of the Weeks-Chandler-Andersen potential and leads to higher-order terms in the respective expansion of the functional around the reference system. The resulting formalism involves weighted densities similar to the ones found in fundamental measure theory. To test our modifications, we analyze and compare density profiles, direct and total correlation functions, and the thermodynamic consistency of the functional via a widely established sum rule and the virial pressure formula for our modified functional, for established functionals, and for data from computer simulations. We found that our modifications clearly show improvements compared to the standard mean-field functional, especially when predicting layering effects and direct correlation functions in high concentration scenarios; for the latter we also find improved consistency when calculated via different thermodynamic routes. In conclusion, we demonstrate how modifications toward higher order corrections beyond mean-field functionals can be made and how they perform, by this providing a basis for systematic future improvements in classical DFT for the description of electrostatic interactions.