Adiabatic versus non-adiabatic electron transfer at 2D electrode materials

Dan-Qing Liu, Minkyung Kang, David Perry, Chang-Hui Chen, Geoff West, Xue Xia, Shayantan Chaudhuri, Zachary P. L. Laker, Neil R. Wilson, Gabriel N. Meloni, Marko M. Melander, Reinhard J. Maurer, Patrick R. Unwin, Nature Communications 12, 7110 (2021)

"Using scanning electrochemical cell microscopy, and co-located structural microscopy, the classical hexaamineruthenium (III/II) couple is measured on a graphene-metal electrode. Using model Hamiltonian and constant potential density functional theory, we can rationalize the fact that monolayer graphene shows faster kinetics than bilayer graphene and we are able to identify the electron transfer as dominantly adiabatic."

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Enhanced Bonding of Pentagon–Heptagon Defects in Graphene to Metal Surfaces: Insights from the Adsorption of Azulene and Naphthalene to Pt(111)

Benedikt P. Klein, S. Elizabeth Harman, Lukas Ruppenthal, Griffin M. Ruehl, Samuel J. Hall, Spencer J. Carey, Jan Herritsch, Martin Schmid, Reinhard J. Maurer, Ralf Tonner, Charles T. Campbell, and J. Michael Gottfried, Chem. Mater. 32, 1041-1053 (2020)

"We show here that the interface properties may be controlled by topological defects, such as the pentagon–heptagon (5–7) pairs, because of their strongly enhanced bonding to the metal. To measure the bond energy and other key properties not accessible for the embedded defects, we use azulene as a molecular model for the 5–7 defect. Comparison to its isomer naphthalene, which represents the regular graphene structure, reveals that azulene interacts more strongly with a Pt(111) surface. Using a combination of single-crystal adsorption calorimetry, x-ray photoelectron and photoabsorption spectroscopies (XPS/NEXAFS), and Density Functional Theory, we fully characterize the adsorption strength, the surface structure and surface chemistry of 5-7 defect systems on Pt(111). Our model study shows that the topology of the π-electron system strongly affects its bonding to a transition metal and thus can be utilized to tailor interface properties."

Many Body Dispersion Effects in the Binding of Adsorbates on Metal Surfaces

R. J. Maurer, V. Ruiz, A. Tkatchenko, J. Chem. Phys., 143, 102808 (2015)

We study the effect of many body dispersion on the geometry and energetics of atoms, molecules and nanostructures adsorbed to a metal surface and find a ubiquitous importance of many body effects to correctly describe adsorbates.