The Role of Water at Electrified Metal-Water Interfaces Unravelled from First Principles

Electrified metal-water interfaces are a key feature in many devices and processes, finding applications in a variety of fields, including corrosion, photo/electrocatalysis, and energy. For over 200 years after Faraday established his ground-breaking law, electrochemistry has been subject to intense research, due to its broad applications and interdisciplinary nature. However, it remains an open challenge to provide a comprehensive description of molecular scale structure and processes at electrified interfaces in electrochemical conditions. In this review, we highlight the most recent advancements in the application of ab initio molecular dynamics (AIMD) to study metal-water interfaces, noting how this work aligns with experimental and other theoretical models. We show how AIMD simulations have unveiled new perspectives on the crucial impact of water on determining surface potentials, the chemistry of surface adsorbates, and capacitive response under electrochemical conditions. We highlight how this work aligns with experimental and other simplified theoretical models.