Abstract
We investigate the surface-catalyzed dissociation of the archetypal molecular switch azobenzene on the Cu(111) surface. Based on X-ray photoelectron spectroscopy, normal incidence X-ray standing waves and density functional theory calculations a detailed picture of the coverage-induced formation of phenyl nitrene from azobenzene is presented. Furthermore, a comparison to the azobenzene/Ag(111) interface provides insight into the driving force behind the dissociation on Cu(111). The quantitative decay of azobenzene paves the way for the creation of a defect free, covalently bonded monolayer. Our work suggests a route of surface functionalization via suitable azobenzene derivatives and the on surface synthesis concept, allowing for the creation of complex immobilized molecular systems.
Highlights
Based on X-ray photoelectron spectroscopy, normal incidence X-ray standing waves and density functional theory calculations a detailed picture of the coverage-induced formation of phenyl nitrene from azobenzene is presented
The quantitative decay of azobenzene paves the way for the creation of a defect free, covalently bonded monolayer
Our work suggests a route of surface functionalization via suitable azobenzene derivatives and the on surface synthesis concept, allowing for the creation of complex immobilized molecular systems
Summary
Components involved, i.e., the anchor-/linker-system and the terminal end group (functional group) In this communication, employing a combination of X-ray photoelectron spectroscopy (XPS), normal incidence X-ray standing waves (NIXSW) and density functional theory (DFT), we demonstrate a coverage-driven quantitative dissociation of azobenzene on Cu(111), leading to the formation of a welldefined covalently bonded and ordered phenyl nitrene monolayer, which can serve as a basis for various surface functionalizations. A threefold hollow adsorption site is consistent with such a small adsorption height; the N–Cu bond length of the new species must be 1.89(7) Å This bond length is similar to the one predicted for the dissociative adsorption of N2 on Cu(111).[17] Together with a mean carbon height of 4.25(4) Å, extracted from the C1s NIXSW yield profiles (see Table 1), this finding indicates that azobenzene must have dissociated to form upright standing phenyl nitrene. Due to the approximate semi-local description of exchange and correlation, the absolute binding energies are systematically underestimated, for which we correct by rigidly shifting our calculated XPS binding energies,
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