Modeling electrified metal/water interfaces from ab initio molecular dynamics: Structure and Helmholtz capacitance

The structure and potential distribution of electric double layers (EDLs) are of close relevance to the performance of electrode materials. In the past years, despite tremendous efforts devoted to this topic, an atomistic picture of the EDL is still lacking, let alone understanding on how the EDL structure is related to the dielectric property of interface water. In this article, we briefly review the recent progress in modeling electrified metal/water interfaces using ab initio molecular dynamics (AIMD). The ab initio methods for EDL modeling is firstly summarized, and then we discuss the structures of interface water on metal electrodes at different potential conditions. Moreover, we illustrate the potential-dependent behavior of chemisorbed water on Pt(111) surface and its relationship with the peak of the differential Helmholtz capacitance observed by experiment. At last, we give some perspective for future development in ab initio modeling of electrochemical interfaces.

Automated summary

In this article, recent progress in modeling electrified metal/water interfaces using ab initio molecular dynamics (AIMD) is reviewed, focusing on the relationship between the structure of electric double layers (EDLs) and the dielectric property of interface water, as well as the variations in the structure of interface water on metal electrodes under different potential conditions. The potential-dependent behavior of chemisorbed water on Pt(111) surface and its correlation with the differential Helmholtz capacitance peak observed by experiment are also elucidated, providing insights for future development in ab initio modeling of electrochemical interfaces.