Abstract
The unique feature of electrochemistry is the ability to control reaction thermodynamics and kinetics by the application of electrode potential. Recently, theoretical methods and computational approaches within the grand canonical ensemble (GCE) have enabled to explicitly include and control the electrode potential in first principles calculations. In this review, recent advances and future promises of GCE density functional theory and rate theory are discussed. Particular focus is devoted to considering how the GCE methods either by themselves or combined with model Hamiltonians can be used to address intricate phenomena such as solvent/electrolyte effects and nuclear quantum effects to provide a detailed understanding of electrochemical reactions and interfaces.
Highlights
Electrochemical reactions take place at extremely complex electrified solideliquid interfaces. The properties of such electrochemical interfaces and reaction thermodynamics and kinetics are controlled by the choice of the electrode material and reaction conditions including the electrode potential (U), temperature (T), and concentrations (c) or equivalentlychemical potentials me
Particular focus is placed on methods to describe electron transfer (ET) and proton-coupled electron transfer (PCET) reactions at electrochemical interfaces, which are crucial in both fundamental and application-oriented electrochemistry [2]
Promising approaches and alternatives in this direction are available from recent quantum dynamics literature on electronic friction or modified fewest switches surface hopping methods [55], which can be combined with (GCEe)density functional theory (DFT) Hamiltonians [56]
Summary
Electrochemical reactions take place at extremely complex electrified solideliquid interfaces. We show that all canonical rate theories can be extended to compute constant potential GCE rates; this construction enables using previous rate theories developed for ‘normal’ chemistry in electrochemistry This important realization facilitates going beyond TST rates to address, for example, tunneling, nonadiabaticity, and solvent dynamics in electrochemical ET/PCET reactions from first principles. This rate theory can be directly combined with GCEeDFT methods to self-consistently include all potential-dependent interactions in the rate constant. Other differences can be found in the used parameters: Huang’s classical model used a high solvent reorganization energy
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