Monte Carlo and HNC/MSA results for an asymmetrical electrolyte in an external electrical field of spherical geometry

Abstract

Results are reported from Monte Carlo (MC) simulations for a model asymmetrical electrolyte, in an external electrical field of spherical geometry. Calculations were made for various 2:1 and 1:2 electrolyte concentrations and field parameters. The hypernetted chain/mean spherical equation (HNC/MSA) is solved for 1:2 and 2:1 salts. The MC results are compared with those from HNC/MSA, the fifth version of the modified Poisson-Boltzmann (MPB5), and Poisson-Boltzmann (PB) theories. Good overall agreement between HNC/MSA and MPB5 results and the MC data is found. On the other hand, the widely used PB theory is found to have important quantitative and qualitative differences from the MC results.