Title: Quantum-continuum simulation of underpotential deposition at electrified metal-solution interfaces,
Abstract: The underpotential deposition of transition metal ions is a critical step in
many electrosynthetic approaches. While underpotential deposition has been
intensively studied at the atomic level, first-principles calculations in
vacuum can strongly underestimate the stability of underpotentially deposited
metals. It has been shown recently that the consideration of co-adsorbed anions
can deliver more reliable descriptions of underpotential deposition reactions;
however, the influence of additional key environmental factors such as the
electrification of the interface under applied voltage and the activities of
the ions in solution have yet to be investigated. In this work, copper
underpotential deposition on gold is studied under realistic electrochemical
conditions using a quantum-continuum model of the electrochemical interface. We
report here on the influence of surface electrification, concentration effects,
and anion co-adsorption on the stability of the copper underpotential
deposition layer on the gold (100) surface.