Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics

Significance The gap preventing a direct comparison between experiment and atomic simulation still exists due to the unrealistic consideration of the operando experimental condition in commonly used quantum mechanics (QM). In this work, we advanced the QM-based simulation of the electrode–electrolyte interface with explicit consideration of solvent and applied voltage to produce reactive trajectories as input for a two-phase thermodynamics model in generating vibrational density of states that can be directly compared with the reported experimental spectroscopy. After resolving the signals, we successfully distinguished the reactive intermediates in a carbon dioxide reduction reaction, which provides an atomic-scale understanding of this important reaction.