Bromine adsorption on Cu(111)

The dissociative chemisorption of molecular bromine on Cu(111) at 300 K has been studied using ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and work function change measurements. A (√3 × √3)R30° structure is formed initially at a bromine coverage of 0.33 ML. This then converts to a (9√3 × 9√3)R30° compression structure with a coverage of 0.41 ML. The coincidence distance of the compression structure is determined entirely by the van der Waals diameter of adsorbed bromine. The applicability of using the van der Waals diameters of the three halogens, Cl, Br and I, to predict the saturation compression structures on Cu(111), is discussed.     

First principle calculations of benzotriazole adsorption onto clean Cu(1 1 1)

The adsorption of benzotriazole (BTAH or C₆N₃H₅) on a Cu(1 1 1) surface is investigated by using first principle density functional theory calculations (VASP). It is found that BTAH can be physisorbed (<0.1 eV) or weakly chemisorbed (∼0.43 eV) onto Cu(1 1 1), and the chemical bond is formed through nitrogen sp² lone pairs. The weak chemisorption can be stabilized by reaction with neighboring protonphilic radicals, like OH⁻. Furthermore, the geometries and associated energies of intermolecular hydrogen bonds between adsorbates on Cu(1 1 1) are also calculated. A model of the first layer of BTAH/BTA⁻ on Cu(1 1 1) surface is developed based on a hydrogen bond network structure.     

The adsorption geometry of sulphur on Ir{1 0 0}: A quantitative LEED study

A quantitative low energy electron diffraction (LEED) analysis has been performed for the p(2 × 2)-S and c(2 × 2)-S surface structures formed by exposing the (1 × 1) phase of Ir{1 0 0} to H₂S at 750 K. S is found to adsorb on the fourfold hollow sites in both structures leading to Pendry R-factor values of 0.17 for the p(2 × 2)-S and 0.16 for the c(2 × 2)-S structures. The distances between S and the nearest and next-nearest Ir atoms were found to be similar in both structures: 2.36 ± 0.01 Å and 3.33 ± 0.01 Å, respectively. The buckling in the second substrate layer is consistent with other structural studies for S adsorption on fcc{1 0 0} transition metal surfaces: 0.09 Å for p(2 × 2)-S and 0.02 Å for c(2 × 2)-S structures. The (1 × 5) reconstruction, which is the most stable phase for clean Ir{1 0 0}, is completely lifted and a c(2 × 2)-S overlayer is formed after exposure to H₂S at 300 K followed by annealing to 520 K. CO temperature-programmed desorption (TPD) experiments indicate that the major factor in the poisoning of Ir by S is site blocking.     

Chemical bonding of PTCDA on Ag surfaces and the formation of interface states

We present a detailed investigation of the interface bonding of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) on Ag(1 1 1) and Ag(1 1 0) surfaces by a combination of structural and electronic techniques (SPA-LEED, STM, TPD, UPS, HR-XPS, and NEXAFS) thus obtaining a consistent picture of the adsorption behaviour of PTCDA/Ag in the monolayer regime. The interaction with silver is strong and leads to the formation of new common hybrid orbitals in the monolayer, which are interface states for PTCDA films on Ag, involving at least LUMO, HOMO, and HOMO-1, and the Ag 5s- and 4d-states. This chemisorption is based on a covalent interaction between metal and molecular states, and can unambiguously be distinguished from mere van-der-Waals bonding.     

Interaction of ethylene with palladium clusters supported on oxidised tungsten foil

The reactivity with ethylene of palladium clusters supported on oxidised tungsten foil has been investigated by synchrotron radiation-induced photoelectron spectroscopy and temperature programmed desorption. The effect of the heat pre-treatment of the sample on the interaction strength with ethylene is demonstrated. Already at room temperature, adsorption of ethylene causes breaking of both the C-H and C-C bonds and the appearance of a highly reactive C₁ phase with unsaturated bonds. A part of this phase is oxidised to carbon monoxide by oxygen supplied by the support immediately after ethylene adsorption. Another part of ethylene is probably adsorbed in the form of ethylidyne. Heating at temperatures between 400 K and 500 K brings about the dissolution of the C₁ phase in the shallow subsurface region of the Pd clusters. Further oxidation of the C₁ phase by oxygen from the support proceeds at ∼600 K. Substantial reduction of the concentration of C₁ phase at room temperature is observed after heat pre-treatment of the sample at 500 K, while complete suppression of the room temperature ethylene chemisorption proceeds upon heat pre-treatment at 800 K. This effect is related to thermally induced encapsulation of palladium clusters in surface tungsten oxide.     

Function of subsurface boron on Si(0 0 1)-2 × 1: water adsorption

Using density functional theory calculations we investigate the function of subsurface boron in determining surface properties of Si(0 0 1). To demonstrate its effect on surface reactivity we compare the behaviors of water adsorption on the clean and B-modified surfaces. We find that subsurface boron brings about a significant change in surface chemical properties by altering charge polarization of Si(0 0 1) locally. As a consequence, water adsorption on the B-modified surface shows a distinctively different feature from that on the clean surface.     

Photon-stimulated ion desorption from DCOO/Si(100) near the O K-edge

Photon-stimulated ion desorption from deuterated formic acid chemisorbed on Si(100) has been studied using pulsed synchrotron radiation in the energy region of the oxygen 1s electron excitation. The O 1s electrons of hydroxyl oxygen and carbonyl oxygen could be selectively excited in the O K-edge region because the chemical environments are different. It is found that the CDO⁺ yield is enhanced at the O 1s(C---O)→σ*(C---O) resonance and the CD⁺ yield at the O 1s(C=O)→σ*(C---O) resonance. The results indicate that ion desorption is related both to the antibonding character of excited molecular orbitals and the local character of core hole orbitals.     

Rare gas coadsorption with Cs or K on Ag(111)

Rare gas (RG) coadsorption with submonolayer amounts of Cs or K on Ag(111) was studied using low-energy electron diffraction (LEED). A crossover in the alkali-RG interaction from repulsive to attractive was observed as a function of alkali species and of alkali coverage. The K---RG interaction was observed to be repulsive at all coverages, while the Cs---RG interaction was observed to be attractive at low Cs coverages and apparently repulsive at high Cs coverages. For the K + RG adsorption system, desorption data were analyzed to determine the spreading pressure in the alkali layer, thus showing that RG can be used as a 2D manometer in some coadsorption systems. From the spreading pressure it is possible to obtain some information about the properties of the adsorbed alkali such as the energy differences between commensurate and incommensurate phases. We also demonstrate that work function measurements from such coadsorption systems do not necessarily have a simple interpretation.     

Adsorption mechanisms of translationally-energetic O2 and N2: direct dissociation versus direct molecular chemisorption

A direct dissociation mechanism has been traditionally assigned to molecular beam data that exhibit an increase in the initial adsorption probability with increasing kinetic energy. Yet, recent experiments of nitrogen and oxygen adsorption provide support for an alternative high kinetic energy pathway in which incident energy assists in surmounting barriers to molecular chemisorption on a surface as the first step to dissociation. Moreover, systems for which the experimental evidence supports such a mechanism also demonstrate that molecularly chemisorbed intermediates can be spectroscopically observed at low temperatures and coverages from exposure to a gas in thermal equilibrium at room temperature. Likewise, such observations have not been measured for systems which are consistent with direct dissociation. A consideration of this trend regarding the existence of molecularly chemisorbed states and the implications for the dominant, dissociative chemisorption pathway at high kinetic energy is presented for a number of gas surface systems.     

Coadsorption of methyl radicals and oxygen on Rh(1 1 1)

The chemisorption of CH₃ on Rh(1 1 1) is studied to understand the origin of the weakened symmetric stretch mode. A few different explanations for this weakened mode have been suggested in previous studies. These include C-H bond depletion and donation into C-H anti-bond orbitals either in an upright or tilted geometry. We investigate these possibilities by performing first-principles density functional calculations. Our results show strong adsorption at all high-symmetry sites with methyl in two possible orientations. A thorough analysis of the adsorption geometry shows that C_3v symmetry is preferred over a tilted species, ruling out tilting as a mechanism for C-H mode softening. Evidence of a multi-center bond between methyl and the surface rhodium atoms (similar to the kind shown recently by Michaelides and Hu for methyl on Ni(1 1 1)) is presented, showing that C-H bond depletion is the cause of mode-softening for methyl on Rh(1 1 1). Experimental results have shown that mode-softening diminishes when an electronegative species is coadsorbed, suggesting that donation into C-H anti-bonding orbitals is the mechanism for mode-softening. We therefore examine the coadsorption of oxygen and methyl on Rh(1 1 1). Our results suggest a new model for the effect of O on CH₃. Analysis of charge density differences shows that the dominant initial effects of O coadsorption are the removal of charge from the C-surface bond and the transfer of charge to the C-H bond. Subsequent increase of the H-Rh distance further reduces mode softening.