SNAPSHOTS OF AN ELECTROCHEMICAL INTERFACE: A STUDY OF THE INTERFACIAL STRUCTURE AT Cu(111) FROM HYDROGEN EVOLUTION THROUGH INITIAL STAGES OF OXIDE FORMATION WITH DFT

摘要

Non-local gradient corrected density functional theoretical calculations are used to determine a series of stationary points for a model copper (111) ?water interface at both anodic and cathodic potentials. The system is described within the periodic slab architecture and is comprised of a model metal-water interface with an interslab spacing of 20 A (rho(H2O)=1.1 g/cm3). Changes in the dipole orientation of interfacial water and the local hydrogen bonding network are correlated with applied charge, and new mechanisms for copper dissolution / oxide precipitation and hydrogen evolution are suggested.