MOLECULAR-SOLVENT MODEL FOR AN ELECTRICAL DOUBLE-LAYER - ASYMMETRIC SOLVENT EFFECTS

Previous reference hypernetted-chain theoretical results for electrica l double layers using a multipolar solvent with tetrahedral geometry a re extended here to a more accurate water model having only C2v symmet ry. This model exhibits a net polarization at a flat uncharged surface with the positive end of the dipoles inclined into the fluid; the res ulting surface potential is compared with both computer simulation and experimental results for the free surface of liquid water. This model also responds differently to positively and negatively charged surfac es, both with and without electrolyte. This leads to an asymmetry in t he differential capacitance of the electrical double layer.