Abstract
Potential-induced changes in charge and surface structure are significant drivers of the reactivity of electrochemical interfaces but are frequently difficult to decouple from the effects of surface solvation. Here, we consider the Cu(100) surface with a c(2 × 2)-Cl adlayer, a model surface with multiple geometry measurements under both ultrahigh vacuum and electrochemical conditions. Under aqueous electrochemical conditions, the measured Cu-Cl interplanar separation (d(Cu-Cl)) increases by at least 0.3 Å relative to that under ultrahigh vacuum conditions. This large geometry change is unexpected for a hydrophobic surface, and it requires invoking a negative charge on the Cl-covered surface which is much greater than expected from the work function and our capacitance measurements. To resolve this inconsistency we employ ab initio calculations and find that the Cu-Cl separation increases with charging at a rate of 0.7 Å/e(-) per Cl atom. The larger Cu-Cl bond distance increases the surface dipole and, therefore, the work function of the interface, contributing to the negative charge under fixed potential electrochemical conditions. Interactions with water are not needed to explain either the large charge or large Cu-Cl interplanar spacing of this surface under electrochemical conditions.