Excluded volume effect of counterions and water dipoles near a highly charged surface due to a rotationally averaged Boltzmann factor for water dipoles.

Water ordering near a negatively charged electrode is one of the decisive factors determining the interactions of an electrode with the surrounding electrolyte solution or tissue. In this work, the generalized Langevin-Bikerman model (Gongadze-Iglič model) taking into account the cavity field and the excluded volume principle is used to calculate the space dependency of ions and water number densities in the vicinity of a highly charged surface. It is shown that for high enough surface charged densities the usual trend of increasing counterion number density towards the charged surface may be completely reversed, i.e. the drop in the counterions number density near the charged surface is predicted.