Physics applied to electrochemistry: Tunneling reactions

In this work, we explore how electrochemical tunneling reactions can be understood within the single-particle picture. That is, the formal approach in which band diagrams are typically utilized to understand electronic processes in solid-state materials and devices. This single-particle perspective is based upon the Gerischer–Hopfield description of electron transfer at solid–liquid interfaces. Both single and multiple electron tunneling reactions are discussed, as are related voltammetric concepts and trends. The impact of nuclear quantization on the Gerischer–Hopfield description is also addressed, as well as its compact representation of two probe electrochemical phenomena at low temperatures (often referred to as Franck–Condon blockade). In this manner, a perspective linking solid-state phenomena and tunneling electrochemical reactions is presented.