Sampyo Hong

A Surface Coordination Network Based on Substrate‐Derived Metal Adatoms with Local Charge Excess

In the quest for increased control and tuneability of organic patterns at metal surfaces, more and more systems emerge that rely upon coordination of metal adatoms by organic ligands using endgroups such as carbonitriles, amines, and carboxylic acids. Such systems promise great flexibility in the size and geometry of the surface pattern through choice of the ligand shape, the number and arrangement of ligating endgroups, and the nature of the metal centers. Planar (trigonal or square) arrangements of ligands around metal centers occur most commonly as a result of attractive interactions of the ligands with the substrate. In contrast, in the solution phase planar, and in particular trigonal planar, arrangements are quite rare and generally require ligands whose nature (for example bidentate, pincer shape) forces planarity. Given the relatively short history of the field of surface coordination chemistry, compared to its solution-phase counterpart, it is of great interest to know which information can be gleaned from the latter to predict that for the former. Aspects of coordination chemistry at surfaces that have attracted very little attention to date are the effective oxidation state of the metal atom, which is much more straightforward to define in the solution phase, and the response of the coordination center to the presence of ligands at a surface. This study details an effort at gaining some insight into these two aspects, using a coordination system which is particularly facile to prepare, as it relies on substrate atoms as coordination centers, rather than requiring their separate deposition. In particular, this study describes the formation of a hexagonal network of 9,10-anthracenedicarbonitrile (DCA) on Cu(111) by titration of a nearly square molecular arrangement with copper atoms released from the substrate by annealing. We apply a combination of experimental and theoretical methods and juxtapose their results with the molecular patterns formed in the absence of a substrate. Individual DCA molecules adsorb flat onto Cu(111) with the anthracene moiety parallel to the high-symmetry direction of the substrate. Figure 1 shows an STM image of DCA

Electronic properties and charge transfer phenomena in Pt nanoparticles on γ-Al2O3: size, shape, support, and adsorbate effects.

This study presents a systematic detailed experimental and theoretical investigation of the electronic properties of size-controlled free and γ-Al(2)O(3)-supported Pt nanoparticles (NPs) and their evolution with decreasing NP size and adsorbate (H(2)) coverage. A combination of in situ X-ray absorption near-edge structure (XANES) and density functional theory (DFT) calculations revealed changes in the electronic characteristics of the NPs due to size, shape, NP-adsorbate (H(2)) and NP-support interactions. A correlation between the NP size, number of surface atoms and coordination of such atoms, and the maximum hydrogen coverage stabilized at a given temperature is established, with H/Pt ratios exceeding the 1 : 1 ratio previously reported for bulk Pt surfaces.

Structural and Electronic Properties of Micellar Au Nanoparticles: Size and Ligand Effects

Gaining experimental insight into the intrinsic properties of nanoparticles (NPs) represents a scientific challenge due to the difficulty of deconvoluting these properties from various environmental effects such as the presence of adsorbates or a support. A synergistic combination of experimental and theoretical tools, including X-ray absorption fine-structure spectroscopy, scanning transmission electron microscopy, atomic force microscopy, and density functional theory was used in this study to investigate the structure and electronic properties of small (∼1-4 nm) Au NPs synthesized by an inverse micelle encapsulation method. Metallic Au NPs encapsulated by polystyrene 2-vinylpiridine (PS-P2VP) were studied in the solution phase (dispersed in toluene) as well as after deposition on γ-Al2O3. Our experimental data revealed a size-dependent contraction of the interatomic distances of the ligand-protected NPs with decreasing NP size. These findings are in good agreement with the results from DFT calculations of unsupported Au NPs surrounded by P2VP, as well as those obtained for pure (ligand-free) Au clusters of analogous sizes. A comparison of the experimental and theoretical results supports the conclusion that the P2VP ligands employed to stabilize the gold NPs do not lead to strong distortions in the average interatomic spacing. The changes in the electronic structure of the Au-P2VP NPs were found to originate mainly from finite size effects and not from charge transfer between the NPs and their environment (e.g., Au-ligand interactions). In addition, the isolated ligand-protected experimental NPs only display a weak interaction with the support, making them an ideal model system for the investigation of size-dependent physical and chemical properties of structurally well-defined nanomaterials.

Origin of the C-induced p4g reconstruction of Ni(001)

First principles calculations of the geometric and electronic structures have been performed for two coverages (0.25 ML and 0.5 ML) of C on Ni(001) to understand the mechanism of the Ni(001) reconstruction induced by carbon adsorption. The calculated structural behavior of the system is in a good agreement with experimental observations. The calculated path and energetics of the

H-atom position as pattern-determining factor in arenethiol films.

c(2\times 2)

Ab initio calculations of adsorbate-induced stress on Ni(100)

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First-principles calculations of the phonon dispersion curves of H on Pt(111)

p4g

Adsorbate induced changes in surface stress and phonon dispersion curves of chemisorbed systems

reconstruction in C

Stress balance in nanopatterned N/Cu(001) surfaces

_{0.5}

First-principles calculations of the dispersion of surface phonons on unreconstructed and reconstructed Pt(110)

/Ni(001) is provided. A dramatic reduction of the local electronic charge on adsorbed carbon is found to occur upon the reconstruction that decreases the electron-electron repulsion on C site. This effect together with the formation of covalent bonds between C and the second layer Ni atoms, leads to reconstruction of Ni(001).