Abstract

A local HNC/HNC and a HNC/HNC (hypernetted-chain) treatment of the double layer for 2:1 electrolytes is presented. The local HNC/HNC treatment produces improved structure information about the double layer. For divalent counter-ions, nonmonotonic co-ion profiles and improved charge inversions near the electrode are obtained as well as improved diffuse layer potentials; for monovalent counter-ions, packing layers build up at high surface charges. These are effects due to the treatment of the ionic correlations in non-neutral homogeneous systems with the local composition of the electrolyte in front of the electrode. At zero surface charge, a nonzero surface potential is obtained.

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