Computational electrochemistry: The boundary element method

The boundary element (BE) method is presented as an efficient and powerful method for the analysis of electrochemical processes. The paper describes t he theory and numerical details required to develop steady state, one-, two -, and three-dimensional diffusional models for voltammetric simulations. T he reduction in dimensionality brought about by the application of BE metho d for processes is noted, along with the resulting benefits when applied to electrochemical systems. The versatility and efficiency of the numerical p rocedures are examined with respect to a number of electrode geometries. In the case of 2D procedures the simulation of a microdisk and microhemispher ical geometries are evaluated and the results compared to the analytical be havior. The change in current density observed as the hemispherical electro de is sequentially flattened to a microdisk is then described. Three-dimens ional simulations focus on modeling a microdisk electrode which is then dis torted. The resulting current density obtained for a range of three-dimensi onal geometries are noted. The potential of the BE method for examining irr egular electrode geometries is also noted.