Spin Manipulation by Creation of Single-Molecule Radical Cations

All-trans-retinoic acid (ReA), a closed-shell organic molecule comprising only C, H, and O atoms, is investigated on a Au(111) substrate using scanning tunneling microscopy and spectroscopy. In dense arrays single ReA molecules are switched to a number of states, three of which carry a localized spin as evidenced by conductance spectroscopy in high magnetic fields. The spin of a single molecule may be reversibly switched on and off without affecting its neighbors. We suggest that ReA on Au is readily converted to a radical by the abstraction of an electron.Comment: 5 pages, 3 figures, accepted for publication in Phys. Rev. Let

Communication : charge-population based dispersion interactions for molecules and materials

We introduce a system-independent method to derive effective atomic C6 coefficients and polarizabilities in molecules and materials purely from charge population analysis. This enables the use of dispersion-correction schemes in electronic structure calculations without recourse to electron-density partitioning schemes and expands their applicability to semi-empirical methods and tight-binding Hamiltonians. We show that the accuracy of our method is en par with established electron-density partitioning based approaches in describing intermolecular C6 coefficients as well as dispersion energies of weakly bound molecular dimers, organic crystals, and supramolecular complexes. We showcase the utility of our approach by incorporation of the recently developed many-body dispersion method [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012)] into the semi-empirical density functional tight-binding method and propose the latter as a viable technique to study hybrid organic-inorganic interfaces

Core electron binding energies in solids from periodic all-electron Δ-self-consistent-field calculations

Theoretical calculations of core electron binding energies are required for the interpretation of experimental X-ray photoelectron spectra, but achieving accurate results for solids has proven difficult. In this work, we demonstrate that accurate absolute core electron binding energies in both metallic and insulating solids can be obtained from periodic all-electron Δ-self-consistent-field (ΔSCF) calculations. In particular, we show that core electron binding energies referenced to the valence band maximum can be obtained as total energy differences between two ( - 1)-electron systems: one with a core hole and one with an electron removed from the highest occupied valence state. To achieve convergence with respect to the supercell size, the analogy between localized core holes and charged defects is exploited. Excellent agreement between calculated and experimental core electron binding energies is found for both metals and insulators, with a mean absolute error of 0.24 eV for the systems considered

Adsorption, Single‐Molecule Manipulation, and Self‐Assembly of Borazine on Ag(111)

Abstract The interaction of borazine with metal supports and the concomitant surface chemistry play important roles in the synthesis of hexagonal boron nitride and the assembly of BN‐doped carbon nanostructures, thus making adsorbed borazine an intriguing model system. Herein, the first real space characterization of individual borazine molecules and highly ordered borazine self‐assemblies on solid supports, combining scanning tunneling microscopy (STM), scanning tunneling spectroscopy, X‐ray photoelectron spectroscopy, and complementary density functional theory modeling is reported. Specifically, a weak, nondissociative adsorption of borazine with the ring aligned in parallel to the surface plane is observed on Ag(111) upon low temperature deposition. Borazine is found to favor hollow adsorption sites, which guide the assembly of intricate borazine assemblies including a porous, chiral honeycomb‐like network, and dense‐packed monolayer films. Additionally, a modification of the borazine adsorption configuration by STM‐based manipulation is demonstrated. Dehydrogenation of individual molecules by voltages pulses yields an upright standing borazine fragment bound via B to Ag. This study thus provides a comprehensive, single‐molecule level characterization of borazine adsorption and surface chemistry on a characteristic coinage metal support and may serve as a reference for advanced low‐dimensional materials based on functionalized borazines or including BN units as dopants

Assembly of Robust Holmium-Directed 2D Metal-Organic Coordination Complexes and Networks on the Ag(100) Surface

We describe the formation of lanthanide-organic coordination networks and complexes under ultra-high-vacuum conditions on a clean Ag(100) surface. The structures comprise single Ho atoms as coordination centers and 1,4-benzenedicarboxylate (from terephtalic acid, TPA) as molecular linkers. Using low temperature scanning tunneling microscopy, we find two different chiral phases of surface-supported metal-organic structures incorporating Ho atoms. Density functional theory calculations can explain the structure of both binding motifs and give possible reasons for their varying formation under the respective Ho/TPA ratios, as well as deposition and annealing temperatures. Metal-ligand interactions drive the formation of cloverleaf-shaped mononuclear Ho-TPA(4) complexes establishing supramolecular arrays stabilized through hydrogen bonding. A 2D lanthanide-organic reticulation is observed when changing the stoichiometry between the two building blocks. The combined insights from scanning tunneling microscopy and density functional theory reveal the relative stability, charge transfer, and bonding environment of both motifs