Influence of size of solvent molecules on structural and thermodynamic properties of the electrode/electrolyte interface

Abstract

The influence of size of solvent molecules on the structural and thermodynamic properties of the interface between the electrode and electrolyte, using the solvent primitive model, was studied by grand canonical Monte Carlo (GCMC) simulations. The computer simulation results are compared with those obtained from the modified Poisson–Boltzmann (MPB) theory. The ionic singlet distribution functions show that the solvent molecules of low diameter favour the counter ion adsorption on the electrode. With increasing diameter of the solvent molecules, the mean electrostatic potential increases, while the integral and differential capacitances decrease. The integral capacitance curves obtained by MPB theory are in qualitative agreement with those obtained by the GCMC simulation although the theoretical results are overestimated.

Keywords:

• solvent primitive model electrolyte
• electrode electrolyte interface
• modified Poisson–Boltzmann theory
• grand canonical Monte Carlo simulation

Acknowledgements

The financial support of Adam Mickiewicz University, Faculty of Chemistry, is appreciated.