  A previously developed field-theoretic model [R.D. Coalson et al., J. Chem.
Phys. 102, 4584 (1995)] that treats core collisions and Coulomb interactions on
the same footing is investigated in order to understand ion size effects on the
partition of neutral and charged particles at planar interfaces and the ionic
selectivity of slit nanopores. We introduce a variational scheme that can go
beyond the mean-field (MF) regime and couple in a consistent way pore modified
core interactions, steric effects, electrostatic solvation and image-charge
forces, and surface charge induced electrostatic potential. We show that in the
dilute limit, the MF and the variational theories agree well with MC simulation
results, in contrast to a recent RPA method. The partition of charged Yukawa
particles at a neutral dielectric interface (e.g air-water or protein-water
interface) is investigated. It is shown that as a result of the competition
between core collisions that push the ions towards the surface, and repulsive
solvation and image forces that exclude them from the interface, a
concentration peak of finite size ions sets in close to the dielectric
interface. We also characterize the role played by the ion size on the ionic
selectivity of neutral slit nanopores. We show that the complex interplay
between electrostatic forces, excluded volume effects induced by core
collisions and steric effects leads to an unexpected reversal in the ionic
selectivity of the pore with varying pore size: while large pores exhibits a
higher conductivity for large ions, narrow pores exclude large ions more
efficiently than small ones.
