Mesoscopic self-structuring on metal surfaces: Geometry and electronic structure

The relation between surface stress and surface reconstruction and the electronic origin of surface stress are briefly discussed. Three examples of stress induced mesoscopic self-structuring on metal surfaces are presented, namely O/Cu(110), Au(111) and Pt(110). While the principles underlying the domain formation on the first two systems seem to be understood quite well, the origin of the periodic hill-and-valley structure of Pt(110) is not yet clear. The confinement of electronic surface states in stress induced quasi-one-dimensional domains was studied recently by photoemission on O/Cu(110) and by scanning tunneling spectroscopy on Au(111). The results are briefly reviewed. The same basic effects were found in the two different studies.     

Local symmetry and chirality of molecular faces

The concept of local symmetry has been applied to faces of planar sites such as carbon–carbon double bonds and aromatic rings with the principal results being as follows. The two faces of a planar site must have the same local symmetry group. This local symmetry group is limited to the polar point groups. For cyclic compounds, directed cycles must have chirotopic faces although the reverse is not necessarily true: chirotopic faces are possible for both directed and undirected cycles. A number of examples are provided to illustrate these results. Received: 30 June 1999 / Accepted: 4 October 1999 / Published online: 19 April 2000     

Interplay between the ionic and electronic density profiles in liquid metal surfaces

First-principles molecular-dynamics simulations have been performed for the liquid-vapor interfaces of liquid Li, Mg, Al, and Si. We analyze the oscillatory ionic and valence electronic density profiles obtained, their wavelengths, and the mechanisms behind their relative phase shift.     

Structure and electronic properties of the surface of alkali metal peroxides

The CRYSTAL09 program with the implemented B3PW hybrid density functional in a localized basis of atomic orbitals is used to determine the atomic and electronic structure of the surface of lithium, sodium, and potassium peroxides. Geometric parameters, surface energies, partial densities of states, electron density distributions, overlap populations, and atomic charges are calculated. It is found that the geometry relaxation has a characteristic depth up to ～10 Å, while the surface states are located in the upper layers at a depth up to ～2.5 Å. Structural displacements of atoms do not exceed ～ 0.2 Å; the charge of the upper surface layers is positive, whereas the energy state shifts relative to the bulk ones can reach ～1 eV. The surface energy of peroxides decreases with an increase in the atomic number of the cation.     

Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces

The surface properties of PtM (M = Co, Ni, Fe) polycrystalline alloys are studied by utilizing Auger electron spectroscopy, low energy ion scattering spectroscopy, and ultraviolet photoemission spectroscopy. For each alloy initial surface characterization was done in an ultrahigh vacuum (UHV) system, and depending on preparation procedure it was possible to form surfaces with two different compositions. Due to surface segregation thermodynamics, annealed alloy surfaces form the outermost Pt-skin surface layer, which consists only platinum atoms, while the sputtered surfaces have the bulk ratio of alloying components. The measured valence band density of state spectra clearly shows the differences in electronic structures between Pt-skin and sputtered surfaces. Well-defined surfaces were hereafter transferred out from UHV and exposed to the acidic (electro)chemical environment. The electrochemical and post-electrochemical UHV surface characterizations revealed that Pt-skin surfaces are stable during and after immersion to an electrolyte. In contrast all sputtered surfaces formed Pt-skeleton outermost layers due to dissolution of transition metal atoms. Therefore, these three different near-surface compositions (Pt-skin, Pt-skeleton, and pure polycrystalline Pt) all having pure-Pt outermost layers are found to have different electronic structures, which originates from different arrangements of subsurface atoms of the alloying component. Modification in Pt electronic properties alters adsorption/catalytic properties of the corresponding bimetallic alloy. The most active systems for the electrochemical oxygen reduction reaction are established to be the Pt-skin near-surface composition, which also have the most shifted metallic d-band center position versus Fermi level.     

Spectrum of electronic excitations due to the adsorption of atoms on metal surfaces

The time-dependent, mean-field Newns-Anderson model for a spin-polarized adsorbate approaching a metallic surface is solved in the wide-band limit. Equations for the time evolution of the electronic structure of the adsorbate-metal system are derived and the spectrum of electronic excitations is found. The behavior of the model is demonstrated for a set of physically reasonable parameters.     

Restricted surface mobility of thiolate-covered metal surfaces: a simple strategy to produce high-area functionalized surfaces

We have studied the self-assembly of thiol monolayers on high-area nanostructured gold surfaces. These surfaces are highly irregular with a fractal dimension close to 2.5. Auger electron spectroscopy and voltammetric data indicate that thiol self-assembly with a maximum surface coverage approximately 1/3 takes place, the same result as that found for smooth gold surfaces. Therefore, neither curvature effects, which would promote higher coverage, nor excluded volume effects, which would result in lower coverage, are present in these irregular surfaces. The high surface area of the bare electrodes exhibits a rapid surface decay in different liquid media that is hindered by alkanethiolate chemisorption. The presence of thiolate SAMs reduces markedly the mass transport surface diffusion of gold adatoms, hindering surface area decay and freezing the system in a metastable state for days. This effect cannot be explained by considering only hydrocarbon-hydrocarbon chain interactions, because it is also observed for ordered arrays of adsorbed S atoms. Therefore, interactions between ordered chemisorbed species at high coverage seem to be responsible for the observed behavior. The thiol-covered high-area metallic substrates can be used to efficiently anchor a large number of molecules, biomolecules, or nanostructures, improving the performance of SAM-based optical and electrochemical devices.     

Molecular point symmetry and the phase of the electronic wave function: Tools for the prediction of critical points of potential energy surfaces

By combining a well-known theorem of Longuet-Higgins on the phase changes of electronic wave functions along loops encircling a conical intersection of potential surfaces, and a recently proven “vertical symmetry theorem” on the relative distributions of point symmetry groups and potential surface critical points in configuration space, a new result is obtained, suitable for the prediction of the presence of a critical point within a domain of configurations.     

Mode-selective excitation of coherent surface phonons on alkali-covered metal surfaces

We demonstrate the mode-selective excitation of coherent phonons at Pt(111) surfaces covered with submonolayer caesium atoms. A burst of 150 fs laser pulses with the repetition rate of 2.0-2.9 THz was synthesized by using a spatial-light modulator, and used for the coherent surface phonon excitation. The coherent nuclear motion was monitored by time-resolved second harmonic generation. By tuning the repetition rate, we succeeded in controlling the relative amplitude of the vibrational coherence of the Cs-Pt stretching mode (2.3-2.4 THz) to that of the Pt surface Rayleigh phonon mode (2.6 or 2.9 THz, depending on the Cs coverage).     

Competing adsorption between hydrated peptides and water onto metal surfaces: from electronic to conformational properties

Inorganic-(bio)organic interfaces are of central importance in many fields of current research. Theoretical and computational tools face the difficult problem of the different time and length scales that are involved and linked in a nontrivial way. In this work, a recently proposed hierarchical quantum-classical scale-bridging approach is further developed to study large flexible molecules. The approach is then applied to study the adsorption of oligopeptides on a hydrophilic Pt(111) surface under complete wetting conditions. We examine histidine sequences, which are well known for their binding affinity to metal surfaces. Based on a comparison with phenylalanine, which binds as strong as histidine under high vacuum conditions but, as we show, has no surface affinity under wet conditions, we illustrate the mediating effects of near-surface water molecules. These contribute significantly to the mechanism and strength of peptide binding. In addition to providing physical-chemical insights in the mechanism of surface binding, our computational approach provides future opportunities for surface-specific sequence design.     

Alkaline-earth overlayers on furrowed transition metal surfaces: An example of tailoring the surface properties

Alkaline-earth (AE) layers adsorbed on furrowed transition metal surfaces are remarkable for a variety of their atomic structures thus offering a good possibility for exploring the interplay between atomic and electronic structures as well as dynamic properties of surfaces. As the coverage increases, the commensurate-incommensurate transition in the AE layers is accompanied by the nonmetal-to-metal transition (NMT) in the films which leads to dramatic changes in characteristics of photoemission and surface diffusion thus enabling one to tailor the surface properties. The calculations for one-dimensionally compressing monolayers elucidate some important features of the NMT in such adsorbed films. These findings have been exploited to develop effective Mg-Ba alloy photocathodes.     

Exact electronic properties in the classically forbidden region of a metal surface

We derive exact properties of the inhomogeneous electron gas in the asymptotic classically forbidden region at a metal–vacuum interface within the framework of local effective potential energy theory. We derive a new expression for the asymptotic structure of the Kohn–Sham density functional theory (KS‐DFT) exchange‐correlation potential energy v_xc(r) in terms of the irreducible electron self‐energy. We also derive the exact asymptotic structure of the orbitals, density, the Dirac density matrix, the kinetic energy density, and KS exchange energy density. We further obtain the exact expression for the Fermi hole and demonstrate its structure in this asymptotic limit. The exchange‐correlation potential energy is derived to be v_xc(z → ∞) = ?α_KS,xc/z, and its exchange and correlation components to be v_x(z → ∞) = ?α_KS,x/z and v_c(z → ∞) = ?α_KS,c/z, respectively. The analytical expressions for the coefficients α_KS,xc and α_KS,x show them to be dependent on the bulk‐metal Wigner–Seitz radius and the barrier height at the surface. The coefficient α_KS,c = 1/4 is determined in the plasmon‐pole approximation and is independent of these metal parameters. Thus, the asymptotic structure of v_xc(z) in the vacuum region is image‐potential‐like but not the commonly accepted one of ?1/4z. Furthermore, this structure depends on the properties of the metal. Additionally, an analysis of these results via quantal density functional theory (Q‐DFT) shows that both the Pauli W_x(z → ∞) and lowest‐order correlation‐kinetic W(z → ∞) components of the exchange potential energy v_x(z → ∞), and the Coulomb W_c(z → ∞) and higher‐order correlation‐kinetic components of the correlation potential energy v_c(z → ∞), all contribute terms of O(1/z) to the structure. Hence correlations attributable to the Pauli exclusion principle, Coulomb repulsion, and correlation‐kinetic effects all contribute to the asymptotic structure of the effective potential energy at a metal surface. The relevance of the results derived to the theory of image states and to KS‐DFT is also discussed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

A chirality indicator for the walls and the surfaces of silica nanotubes

Single-handed helical silica nanotubes were prepared according to the literature procedures,using the self-assemblies of a pair of chiral cationic low-molecular-weight gelators as the templates.A chirality indicator,4,4’-bis(triethoxysilyl)-1,1’-biphenyl,was developed to determine the chirality of the silica nanotubes.The chirality of the surfaces and the bulky walls of the silica nanotubes were understood from the twist of the biphenylene rings.     

Exploring the electronic structure of elemental lithium: from small molecules to nanoclusters, bulk metal, and surfaces

Clusters of lithium atoms ranging in size from Li4 to Li40 and bulk metallic solids, including surfaces, are investigated through first principles electronic structure calculations, which are based upon density functional theory and the electron localization function (ELF). It is found that large lithium ppi-type contributions in the electronic wavefunction cause the electrons to localize in interstitial regions, which leads to multicenter bonding for both the clusters and the solids, including their surfaces. For the smaller clusters these stabilizing ppi interactions also lead to short Li-Li interatomic distances, which in conjunction with the longer bonds induces "distance alternation" in the range from 2.45 A to 3.15 A. This consequence of the additional ppi interactions is absent in simple solids due to symmetry. The electronic structure of the clusters is topologically insensitive to deformations that do not affect their general shape, but changes significantly upon isomerization. The ramifications upon dynamic properties is that the clusters are quasi-rigid at low temperatures and retain their shape though the distance alternation pattern is suppressed. The picture which emerges for bonding in the bulk solid is that the metallic state arises from the presence of a large number of partially occupied multicenter bonds. For nanoscale clusters only the surface of these clusters exhibits strong localization, whereas their interiors display localization properties similar to the bulk metallic solid. On the other hand, localized states similar to those of the clusters ("dangling bonds") are found on the (001) surface of body-centered cubic (bcc) and face-centered cubic (fcc) lithium solids.     

Transfer of chirality from ligands to metal centers: recent examples

Recent examples of "chiral at metal" complexes and assemblies that are produced by chirality transfer of information from enantiopure ligands to metal ions are reported. They highlight the new progress that has been made in this area in the last two years and the new tendencies that such a topic is following. Besides the fundamental aspects related to the stereoselective synthesis of chiral complexes, the progress in diverse classes of chiral complexes for applications in materials science (chiral switches and molecular machines, biological mimics, CPL probes, etc.) is reported.     

Controlling the position of functional groups at the liquid/solid interface: impact of molecular symmetry and chirality

With the aim of controlling the position of functional groups in a substrate-supported monolayer, a new family of functionalized linear alkyl chains was designed and synthesized, aided by molecular mechanics and dynamics simulations of its two-dimensional self-assembly on graphite. The self-assembly of these amino functionalized diamides at the liquid/solid interface was investigated with scanning tunneling microscopy. Intermolecular hydrogen-bonding interactions involving amides, combined with the effect of molecular symmetry and chirality, were found to guide the self-assembly. Control of the relative position and orientation of the amine groups was achieved, in the case of enantiopure compounds. Interestingly, racemates led to both racemic conglomerate and solid solution formation, with a concomitant loss of positional and orientational control of the amino groups as a result.     

环香叶烷型化合物在金属团簇表面吸附的结构和电子性质

采用密度泛函理论中的B3LYP方法对环香叶烷型代表性化合物紫罗兰酮进行了理论研究,尤其是研究了其在银团簇表面吸附的几何结构、电荷转移、红外光谱和电子亲和能等性质.结果表明,α-紫罗兰酮的吸附位点在C=O键上,而β-紫罗兰酮吸附位点在C=C(主要)和C=O键上,并且这两种结构上的电荷都转移向银团簇,说明此银团簇可以作为较强的吸电子基存在.同时,由于银团簇较强的吸电子特性,导致红外光谱发生"红移".研究也发现两种紫罗兰酮在团簇表面的吸附使得其电子亲和能变大,电离能变小,而吸附能的计算结果表明α-紫罗兰酮与银团簇形成的配合物更加稳定.这些研究为探索其在化学和医学领域的潜在应用提供了重要的理论参考.     

Stabilization of surface reaction intermediates by added metal atoms on metal surfaces of low free energy

Dynamic restructuring of the Ag(111) surface occurs during the reaction of sulfur dioxide with Ag(111)-p(4 x 4)-O at 300 K, resulting in the incorporation of added silver atoms into the unit cells of both adsorbed sulfite and sulfate. This result clearly demonstrates that incorporation of metal atoms into the structures of adsorbates and reaction intermediates is not restricted to more open, higher free energy single crystal planes. These observations indicate that the participation of added metal atoms must be considered in the theoretical treatment of metal catalyzed reactions.