Electronic structure calculations on electrolyte-electrode interfaces: Successes and limitations

Density functional theory calculations on electrolyte-electrode interfaces are briefly reviewed in this article. The calculation methods are roughly categorized into two types: calculations on electrically neutral surfaces and electrified surfaces. The former methods have been successfully applied to reproduce observed trends in catalytic activities and to design new materials. The methods, however, cannot evaluate any electrochemical properties originated from surface electrifications. By this reason, several theoretical methods on electrified interfaces have been proposed. The methods can provide properties originated from charge transfers, such as electrosorption valency values, symmetry factors and potential-dependent spectroscopies, within self-consistent manners. Many limitations, however, still exist, and further studies are necessary particularly on effects of dynamical atomic motions on free energies.