Monolayer adsorption of water on NaCl(1 0 0)

Density functional theory calculations have been applied to investigate the adsorption geometry of water overlayers on the NaCl(1 0 0) surface in the monolayer regime. Competition between H-H intermolecular repulsion and the attraction of the polar molecules to the surface ions results in the most stable structure having a 2 × 1 adsorption symmetry with an adsorption energy of 415 meV. Overlayers of 1 × 1 symmetry, as observed in experiment, have slightly lower adsorption energies. The layers are also unstable with respect to rotation of individual molecules. Multiple hydrogens/oxygens interacting with a single substrate ion can pull that ion out of the surface, although the examples considered are energetically very unfavourable. Overlayers of 1 × 1 symmetry with a coverage of one water molecule per NaCl do not have a high enough adsorption energy to wet the surface.     

Growth and characterization of thin PTCDA films on 3C-SiC(0 0 1)c(2 × 2)

The growth of thin 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) films on a 3C-SiC(0 0 1)c(2 × 2) substrate has been studied by means of photoelectron spectroscopy (PES) and atomic force microscopy (AFM). In the first monolayer the molecules interact with the substrate mainly through the O atoms in the end groups of the molecule. The O atoms have a higher binding energy in the first molecular layer compared to the following layers. No chemical shifts are observed in the Si 2p spectra or in the C 1s spectra from the perylene core of the molecules. From the VB spectra and LEED pattern we conclude that the substrate remains in the c(2 × 2) reconstruction after PTCDA deposition. For thicker films a Stranski-Krastanov film growth was observed with flat lying molecules relative to the substrate.     

Self-assembly of 2,6-dimethylpyridine on Cu(1 1 0) directed by weak hydrogen bonding

Sequential stages of formation of a self-assembled monolayer of flat-lying 2,6-dimethylpyridine molecules on a single crystal Cu(1 1 0) surface have been observed by low-temperature scanning tunneling microscopy (LT-STM). At an adsorption temperature of 10 K, all of the molecules are randomly distributed at low coverage upon adsorption. The isolated molecules align their molecular axes parallel to the 〈0 0 1〉 azimuth of the Cu lattice. The nitrogen atom in the molecule is located at the four-fold hollow site. Upon annealing to 100 K, the molecules associate to form head-to-head dimers. The dimer units involve a pair of weak hydrogen bonds between methyl group-hydrogen atoms and N moieties on adjacent molecules, forming a core structure for further growth. In a later stage of self-assembly, single head-to-tail weak hydrogen bonds between ring C-H bonds and N moieties form in chains on the periphery of the central cores, leading to larger domains with a c(6 × 2) overlayer structure.     

para-Sexiphenyl thin film growth on Cu(1 1 0) and Cu(1 1 0)-(2 × 1)O surfaces

We present a reflectance difference spectroscopy (RDS) study of para-sexiphenyl (p-6P) thin film growth on Cu(1 1 0) and Cu(1 1 0)-(2 × 1)O substrates. The RDS spectra show pronounced anisotropies for p-6P films formed on both substrates at room temperature, demonstrating that the molecules are uniaxially aligned within the films. Based on the RD spectra and the evolution of the optical transitions with p-6P coverage the growth mode on both substrates could be identified. From the dominating RDS feature, assigned to the lowest energy HOMO-LUMO transition, the orientation of the molecular chain can be determined. On Cu(1 1 0), the p-6P molecular chains align in the direction, i.e., along the Cu atomic rows, whereas on the Cu(1 1 0)-(2 × 1)O surface, the molecules are oriented in the orthogonal [0 0 1] direction, i.e., along the “added” Cu-O rows of the Cu(1 1 0)-(2 × 1)O surface. The energetic position and line shape of the main RDS feature differs for the two substrates and varies with p-6P coverage. This fine structure is discussed in terms of different molecular conformations, adlayer structure and vibronic replicas.     

Comparative study of H2 adsorption on W(1 0 0)-c(2 × 2)Cu and W(1 0 0): Surface alloying effects

The interactions of H and H₂ with W(1 0 0)-c(2 × 2)Cu and W(1 0 0) have been investigated through density functional theory (DFT) calculations to elucidate the effect of Cu atoms on the reactivity of the alloy. Cu atoms do not alter the attraction towards top-W sites felt by H₂ molecules approaching the W(1 0 0) surface but make dissociation more difficult due to the rise of late activation barriers. This is mainly due to the strong decrease in the stability of the atomic adsorbed state on bridge sites, the most favourable ones for H adsorption on W(1 0 0). Still, our results show unambiguously that H₂ dissociative adsorption on perfect terraces of the W(1 0 0)-c(2 × 2)Cu surface is a non-activated process which is consistent with the high sticking probability found in molecular beam experiments at low energies.     

Structure of enantiopure and racemic alanine adlayers on Cu(1 1 0)

Plane wave density functional theory has been employed to analyze the structure of alanine adlayers on the Cu(1 1 0) surface. Alanine forms (3 × 2) adlayers on Cu(1 1 0) that are closely related to the structures of glycine on the same surface. There is essentially no energy difference between the most stable racemic and enantiopure alanine adlayers. This observation implies that adsorption of racemic alanine on Cu(1 1 0) will result in a pseudoracemate adlayer.     

Atomic structure and tip-induced reconstruction of bromide covered Cu(1 1 0) electrodes

The behavior of specifically adsorbed bromide on Cu(1 1 0) in 10 mM HBr has been studied using cyclic voltammetry in combination with high resolution in situ electrochemical scanning tunneling microscopy (EC-STM).At cathodic potentials near the onset of the hydrogen evolution reaction the structure of the bare copper surface was observed by EC-STM. A variation of the electrode potential in positive direction causes a specific anion adsorption leading to the formation of a highly ordered superstructure with a quasi-hexagonal symmetry. The two-dimensional lattice of this adlayer can be described by a c(3 × 2) unit cell. The bromide anions are arranged parallel to the close packed copper rows and are located in three different types of adsorption sites. These inequivalently bound bromide species are imaged with different brightness in the STM-pictures. As a result the bromide adlayer exhibits a long-ranged wavy superstructure superimposed on the atomic corrugation.Tip induced copper corrosion is used to obtain highly ordered nanostructures due to a locally confined electrochemical annealing process proceeding along the [0 0 1]-direction of the substrate. This annealing process results in the formation of Cu(1 0 0)-facets.     

Anchoring sulphur-headgroup organic molecules at Cu(1 0 0): Tailoring the interface electronic states

Sulphur-headgroup organic molecules have been chemisorbed on Cu(1 0 0) as self-assembled monolayers (SAMs) in highly-ordered two-fold symmetry structures, and the electronic states induced at the interface have been measured by photoemission: a close similarity of the main interface states for methane-thiolate and mercaptobenzoxazole on Cu(1 0 0) in the same p(2 × 2)-phase is observed. The bonding states for methane-thiolate/Cu(1 0 0) in the p(2 × 2) and c(2 × 2) structures have been compared to ab-initio calculation of the total density of states (DOS) for the S/Cu(1 0 0) system in the same phases. The major role of the S-Cu bonding to determine the density of state evolution at the interface is brought to light. The observed differences in the two phases depend mainly on the charge distribution associated to the different molecular packing, with a minor role of the radical group.     

Supramolecular assembly of biphenyl dicarboxylic acid on Au(1 1 1)

We investigate the structure of submonolayer film of 4,4′-biphenyl dicarboxylic acid (BDA) molecules on Au(1 1 1)-22 × √3 reconstructed surface with the use of scanning tunneling microscopy (STM). The BDA molecules form ordered structures on Au(1 1 1) surface which are commensurate with the substrate. We have concluded that the molecule-molecule interaction is mainly through hydrogen bonding formed by a straight dimer of BDA molecules. The straight dimer can be expressed as 4s + 2t or its six crystallographic equivalents using the unit vectors of the gold substrate of s and t. The length of hydrogen bonding (O-H-O) is estimated to be 0.31 nm assuming nearest neighbor distance of gold atoms of 0.275 nm. The ordering shows a clear contrast with the case of BDA on Cu(1 0 0) surface [S. Stepanow, N. Lin, F. Vidal, A. Landa, M. Ruben, J.V. Barth, K. Kern, Nanoletters 5 (2005) 901] in which a square type of ordering of molecules is observed by the formation of hydrogen bonding between a carboxylate (COO) and a benzene ring. The clear difference of the ordered structure on Cu(1 0 0) and Au(1 1 1) surface demonstrates that the absence (presence) of deprotonation of carboxyl group of BDA molecule on Au(1 1 1) (Cu(1 0 0)) switches the straight and square type ordering of BDA molecules.     

STM study of Bi-on-Cu(1 0 0)

Scanning tunneling microscopy (STM) has been used to study the various possible structures of adsorbed Bi on the Cu(1 0 0) surface, after equilibration at a temperature of 520 K. All of the structures previously identified by X-ray diffraction (lattice gas, c(2 × 2), c(9√2 × √2)R45°, and p(10 × 10), in order of increasing Bi-coverage) were found to be present on a single sample produced by diffusing Bi onto the Cu(1 0 0) surface from a 3-d source. By investigating the possible coexistence of various pairs of phases, it was demonstrated that the c(2 × 2) phase transforms to the c(9√2 × √2)R45° phase by a first order transition, whereas the transition from c(9√2 × √2)R45° to p(10 × 10) is continuous. In addition, the structure of surface steps was studied as a function of Bi-coverage. The results showed that the presence of Bi changes the nature of the step-step interactions at the Cu(1 0 0) surface from repulsive to attractive. The attractive step-step interactions transform any small deviations from the nominal (1 0 0) orientation of the Cu substrate into (3 1 0) microfacets. When compared with the known equilibrium crystal shape (ECS) of Bi-saturated Cu, the observed microfaceting may imply that the ECS of Cu-Bi alloys is temperature dependent.     

Initial stages of oxidation of Cu(1 1 1)

Several surface analysis techniques were combined to study the initial stages of oxidation of Cu(1 1 1) surfaces exposed to O₂ at low pressure (<5 × 10⁻⁶ mbar) and room temperature. Scanning tunneling microscopy (STM) results show that the reactivity is governed by the restructuring of the Cu(1 1 1) surface. On the terraces, oxygen dissociative adsorption leads to the formation of isolated O adatoms and clusters weakly bound to the surface. The O adatoms are located in the fcc threefold hollow sites of the unrestructured terraces. Friedel oscillations with an amplitude lower than 5 pm have been measured around the adatoms. At step edges, surface restructuring is initiated and leads to the nucleation and growth of a two-dimensional disordered layer of oxide precursor. The electronic structure of this oxide layer is characterised by a band gap measured by scanning tunneling spectroscopy to be ∼1.5 eV wide. The growth of the oxide islands progresses by consumption of the upper metal terraces to form triangular indents. The extraction of the Cu atoms at this interface generates a preferential orientation of the interface along the close-packed directions of the metal. A second growth front corresponds to the step edges of the oxide islands and progresses above the lower metal terraces. This is where the excess Cu atoms extracted at the first growth front are incorporated. STM shows that the growing disordered oxide layer consists of units of hexagonal structure with a first nearest neighbour distance characteristic of a relaxed Cu-Cu distance (∼0.3 nm), consistent with local Cu₂O(1 1 1)-like elements. Exposure at 300 °C is necessary to form an ordered two-dimensional layer of oxide precursor. It forms the so-called “29” superstructure assigned to a periodic distorted Cu₂O(1 1 1)-like structure.     

Photoemission study of the (2 × 2) structure formed by H2O adsorption on the Zr(0 0 0 1) surface

We have studied adsorption of water on the Zr(0 0 0 1) surface at sub-monolayer coverage by means of LEED and photoemission spectroscopy. An ordered (2 × 2) structure is formed after adsorption of 0.6-1.4 Langmuirs at 473 K. The sharpest LEED pattern was observed at an exposure of 1.2 L implying a coverage of 0.5 ML of oxygen. The same exposure at 293 K gives only a weak and diffuse (2 × 2) pattern. In addition, the sharp (2 × 2) pattern obtained at 473 K can be reversibly weakened by cooling to 293 K and subsequently sharpened by heating. For the sharp (2 × 2) structure, valence band spectra indicated dissociation of water and showed a peak composed mainly of O 2p derived states with two components at 6.0 eV and 6.6 eV binding energy. On cooling to 293 K, the O 2p peak became narrower and a new state appeared at 7.9 eV. Two components of the O 1s core level were resolved for the (2 × 2) structure, assigned to oxide and hydroxyl groups. The hydrogen on the surface of Zr(0 0 0 1) resulting from the dissociation of water and from bulk segregation strongly influenced the formation of the (2 × 2) structure of oxygen, and caused a temperature instability of the structure.     

LCAO study of the Cu(1 1 0)-p(2 × 1)O surface

We have performed semi-empirical LCAO calculations of the electronic structure of the Cu(1 1 0)-p(2 × 1)O surface. This has been done accounting for the Cu-Cu interactions by means of a recently proposed set of parameters, which give very good results for the bulk as well as for the surfaces of lowest Miller indices. Furthermore, the O-O interactions, which have been neglected in the preceding similar studies, have been taken into account. The resulting surface bands are in very good agreement with the overall set of the available experimental data. Several issues concerning the physical properties of this surface are addressed in the present paper: the changes induced on the clean surface bands by the adsorption and the reconstruction; the arrangement of the Cu and O atoms in the added rows; the position of the p_y antibonding band of the oxygen. In particular, we have found that the latter has an energy of −0.2 eV at the point. This result confirms an experimental indication in the same direction previously reported by Courths et al. [R. Courths, S. Hüfner, P. Kemkes, G. Wiesen, Surf. Sci. 376 (1997) 43].     

Local structure determination of a chiral adsorbate: Alanine on Cu(1 1 0)

N 1s and O 1s scanned-energy mode photoelectron diffraction (PhD) has been used to investigate the local structure of a single enantiomer of deprotonated alanine, alaninate, NH₂CH₃CHCOO-, on Cu(1 1 0) in the (3 × 2) phase. The local site is found to be similar to that of glycinate on Cu(1 1 0), with the N atoms in near-atop sites and the O atoms sites consistent with bonding to single surface Cu atoms but substantially off-atop. Unlike the Cu(1 1 0)(3 × 2)pg-glycinate phase, however, in which the two molecular species per unit mesh are mirror images of one another in identical local sites, the intrinsic chirality of l-alaninate means that the two molecules per unit mesh of the (3 × 2) surface phase occupy slightly different local sites. However, an excellent fit to the PhD data can be achieved by a minor modification of the structure found in DFT calculations by R.B. Rankin and D.S. Sholl [Surf. Sci. 574 (2005) L1] in which the heights of the N and O atoms above the surface are reduced by approximately 0.1 Å. The resulting average N-Cu and O-Cu values are 2.02 and 1.98 Å, respectively, with an estimated precision of ±0.03 Å. These bondlengths are shorter than those obtained from DFT by 0.08 and 0.10 Å, respectively.     

Surface structures of atomic hydrogen adsorbed on Cu(1 1 1) surface studied by density-functional-theory calculations

The surface structures of atomic hydrogen adsorbed on Cu(1 1 1) surface have been studied theoretically by using density-functional-theory calculations. The results show that 0.67 ML hydrogen adsorbed on threefold hollow sites forming (3 × 1) superstructure and 0.5 ML hydrogen adsorbed on threefold hollow sites forming (2 × 2)-2H superstructure with central H at trigonal sites induce most significant substrate reconstructions and that fits best the observed (3 × 3) and (2 × 2) LEED patterns, respectively. The potential energies for the hydrogen in these two models are also lower than those in other competing models. Accordingly, these two models are the most preferable structures for 0.5-0.67 ML and 0.3-0.5 ML hydrogen adsorbed on the Cu(1 1 1) surface. In addition, the calculations also suggest that the lateral H-H interaction is not of simple repulsion and how the adsorbed hydrogen is arrayed is important in modifying the adsorption energy.     

Adsorption model determination of N2O/Ag(1 1 0) by theoretical studies of near-edge X-ray absorption fine structure

The nitrogen 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of the N₂O adsorbed on Ag(1 1 0) have been studied by the multiple-scattering cluster (MSC) and self-consistent field (SCF) DV-Xα methods. Two adsorption models, in which the N₂O molecule attached to the Ag substrate through the central nitrogen (N_C) atom and the terminal nitrogen (N_T) atom, respectively, have been checked up thoroughly. The MSC calculation and the R-factor analysis show that the N₂O molecule is attached to the Ag substrate through the terminal nitrogen atom with the adsorption height h = 3.4 ± 0.1 Å. In the overlayer the N₂O molecules arrange themselves into a tilted chain due to the interaction between the cations and the anions in the molecules. The physical cause of the resonances in the NEXAFS spectra mentioned above has been discussed by the DV-Xα method, which confirms the MSC calculations.     

Theoretical STM images of alkaline-earth metal adsorbed Si(1 1 1)3 × 2 surfaces

We have performed total-energy calculations to study theoretical scanning tunneling microscopy (STM) images of the Si(1 1 1)3 × 2 surfaces induced by the adsorption of alkaline-earth metals (AEMs). Previously, in a series of works on Ba/Si(1 1 1) system, we have found that the observed Si(1 1 1)3 × 1-Ba LEED phase indeed has a 3 × 2 periodicity with a Ba coverage of 1/6 ML and the HCC substrate structure. Based on results of the Ba case, we proposed that the HCC structure is also adopted for other AEM atoms, which was confirmed by our recent work. In this paper, we mainly report the STM simulations for different AEM systems to compare with existing experimental data. We discuss the difference in the detailed STM images for different AEM adsorbates. Especially, the difference in filled-state images between Mg and other AEM atoms is attributed to the strong Mg-Si interaction.     

Molecularly intact and dissociative adsorption of water on clean Cu(1 1 0): A comparison with the water/Ru(0 0 1) system

An X-ray photoelectron spectroscopy (XPS) study was undertaken of the water/Cu(1 1 0)-system finding non-dissociative adsorption on clean Cu(1 1 0) at temperatures below 150 K. Thermally induced dissociation of D₂O is observed to occur above 150 K, similar to the H₂O/Ru(0 0 1) system, with an experimentally derived activation barrier of 0.53-0.56 eV which is very close in magnitude to the derived activation barrier for desorption of 0.50-0.53 eV. X-ray and electron induced damage to the water overlayer was quantified and used to rationalize the results of a recent XPS study of the water/Cu(1 1 0)-system where partial dissociation was observed already at 90 K.     

Asymmetric adsorption-site of potassium atoms in the (3 × 2)-p2mg structure formed on Cu(0 0 1)

The adsorption of K atoms on Cu(0 0 1) has been studied by low-energy electron diffraction (LEED) at room temperature (RT) and 130 K. At RT, a (3 × 2)-p2mg LEED pattern with single-domain was observed at coverage of 0.33, whereas the orthogonal two-domain was found at 130 K. At 130 K, a c(4 × 2) pattern with orthogonal two-domain was observed at coverage 0.25. Both the (3 × 2)-p2mg and c(4 × 2) structures have been determined by a tensor LEED analysis. It is demonstrated that K atoms are adsorbed on surface fourfold hollow sites in the c(4 × 2), while in the (3 × 2) structure two K atoms in the unit cell are located at an asymmetric site with a glide-reflection-symmetry. The asymmetric site is at near the midpoint between the exact hollow site and bridge-site but slightly close to the hollow site. A rumpling of 0.07 Å in the first Cu layer was confirmed, which might stabilize K atoms at the asymmetric site. Surface structures appearing in a coverage range 0.25-0.33 are discussed in terms of the occupation of the asymmetric site with increase of coverage.     

Density functional study of ethylamine and allylamine on Si(1 0 0)-2 × 1 and Ge(1 0 0)-2 × 1 surfaces

We have investigated the interactions of ethylamine and allylamine with models of the Si(1 0 0)-2 × 1 and Ge(1 0 0)-2 × 1 semiconductor surfaces. Ab initio molecular orbital calculations, along with density functional theory (DFT), are used to examine the interaction of these amines with cluster models of the semiconductor surfaces. The transition states and final adsorption products for adsorption of the molecules are predicted. The DFT calculations show the amines form N-dative bond states with Si(1 0 0)-2 × 1 or Ge(1 0 0)-2 × 1 as the initial adsorption product. The initial dative-bond products can be further activated, resulting in N-H bond cleavage on both surfaces. The overall reaction of a given amine on Si(1 0 0) via N-H dissociation is more exothermic than on the Ge(1 0 0) surface.