1 Department of Physics, Technical University of Denmark2 Theoretical Atomic-scale Physics, Department of Physics, Technical University of Denmark3 Center for Atomic-scale Materials Design, Center, Technical University of Denmark4 Department of Energy Conversion and Storage, Technical University of Denmark5 Center for Nanostructured Graphene, Center, Technical University of Denmark
Alignment of metal and molecular electronic energy levels at electrode-electrolyte interfaces is investigated using density functional theory. Three different regimes exhibiting qualitatively different energy level alignments are observed. The regimes are roughly defined by the size of the metal work function relative to the ionization potential and/or electron affinity of the electrolyte. It is demonstrated that proper matching of these quantities is essential for successful ab initio modeling of electrochemical interfaces and it is further discussed how such matching can be obtained by careful tailoring of the interfacial atomic structure.
Chemical Physics Letters, 2013, Vol 555, p. 145-148
Alignment; Density functional theory; Ionization potential; Molecular electronics; Electrolytes