Pepa Cabrera-Sanfelix

Orthogonal Interactions of CO Molecules on a One-Dimensional Substrate

We investigate the chemisorption structure of CO molecules on the quasi-one-dimensional Cu(110)-(2 × 1)-O surface by low-temperature scanning tunneling microscopy and density functional theory. Contrary to flat metal surfaces, where CO molecules adsorb in an upright geometry and interact through repulsive intermolecular interactions, we find the most stable adsorption structure of single CO molecules to be at Cu atoms of substrate Cu-O- chains with the Cu-CO unit bent by ~±45° in two equivalent structures at low coverages. At higher coverages, CO molecules combine in the same structure into highly ordered single-molecule-wide rows perpendicular to the substrate chains in an approximately 8 × 1 full monolayer structure. First-principles calculations attribute the unprecedented chemisorption behavior of CO molecules to lifting of the host Cu atoms by 1 Å from the surface Cu-O- chains, in order to optimize the bonding and reduce the repulsive interactions with the substrate. This structural distortion enables short-range intermolecular dipole-dipole attraction and creates orthogonal long-range surface-mediated repulsion leading to unusual self-assembly of CO molecules into coherent nanometer scale molecular grating structures.

On the structure of the first hydration layer on NaCl(100): Role of hydrogen bonding

The authors have investigated the structure and energetics of the first hydration layer on NaCl(100) by means of density functional calculations. They have analyzed in detail the role of the hydrogen bond between the adsorbed molecules for the determination of the most favorable structures. They have shown that, using the water dimers as basic building blocks, very stable structures can be constructed. They discuss here two important examples: (i) a model with (1x1) periodicity at 2 ML coverage, and (ii) icelike bilayers with a c(4x2) unit cell at 1.5 ML. Both structures present high adsorption energies per water molecule of approximately 570 meV, in comparison to the 350 meV adsorption energy obtained for the previously studied (1x1) structures composed of weakly interacting monomers. Based on these findings, they propose an interpretation for the experimental observations of Toennies et al. [J. Chem. Phys. 120, 11347 (2004)], who found a transition of the periodicity of the first hydration layer on NaCl(100) from (1x1) to c(4x2) upon electron irradiation. According to the model, the transition would be driven by the partial desorption of (1x1) bilayer structures corresponding to a local coverage of 2 ML and the further rearrangement of the remaining water molecules to form a quasihexagonal structure with c(4x2) periodicity at coverage close to 1.5 ML.

Consecutive Mechanism in the Diffusion of D2O on a NaCl(100) Bilayer

The motion of D2O monomers is investigated on a NaCl(100) bilayer on Ag(111) between 42.3 and 52.3 K by scanning tunneling microscopy. The diffusion distance histogram reveals a squared diffusion lattice that agrees with the primitive unit cell of the (100) surface. From the Arrhenius dependence, we derive the diffusion energy, the pre-exponential factor, and the attempt frequency. The mechanism of the motion is identified by comparison of the experimental results to theoretical calculations. Via low temperature adsorption site determination in connection with density functional theory, we reveal an influence of the metallic support onto the intermediate state of the diffusive motion.

Substrate-induced cooperative effects in water adsorption from density functional calculations

Density Functional Theory calculations are used to investigate the role of substrate-induced cooperative effects on the adsorption of water on a partially oxidized transition metal surface, O(2x2)/Ru(0001). Focussing particularly on the dimer configuration, we analyze the different contributions to its binding energy. A significant reinforcement of the intermolecular hydrogen-bond (H-bond), also supported by the observed frequency shifts of the vibration modes, is attributed to the polarization of the donor molecule when bonded to the Ru atoms in the substrate. This result is further confirmed by our calculations for a water dimer interacting with a small Ru cluster, which clearly show that the observed effect does not depend critically on fine structural details and/or the presence of co-adsorbates. Interestingly, the cooperative reinforcement of the H-bond is suppressed when the acceptor molecule, instead of the donor, is bonded to the surface. This simple observation can be used to rationalize the relative stability of different condensed structures of water on metallic substrates.