Quantum Rate Dynamics for Coherent Electron Transport at Material/Electrolyte Interfaces

Nanoscale electronics and electrochemistry are both based on the fundamental principles of electron motion at the material/electrolyte interfaces. Despite this common ground, these fields use distinct conceptual frameworks: physicists favor coherent electron transport, while chemists rely on kinetic electron transfer. In this work, we present the fundamental quantum-mechanical principles that unify these approaches, linking quantum transport to the electron-transfer rate constant in an electrolyte environment. We show that─even at room temperature─electron motion between quantum states, which appears as a slow kinetic rate, is in fact driven by underlying coherent quantum dynamics, modulated by the electrolyte's damping. This coherent transport determines the kinetics of redox switches, controls biological processes such as Geobacter respiration, enables the development of <i>in situ</i> spectroscopic techniques, and accounts for the charge dynamics observed in reduced graphene oxide supercapacitance. As a result, these approaches provide a way to measure the electronic structure of quantum dots and graphene at energies below the radio frequency range. In light of these findings, we discuss the limitations of the traditional reorganization energy (λ₀), which has been used to quantify the low-frequency rate of reaction dynamics in electrochemistry, and propose its replacement with measurable quantum circuit parameters intrinsic to the material's electronic structure.