A.J Jaworowski

Vibrational fine structure in the C 1s photoemission spectrum of the methoxy species chemisorbed on Cu(100)

The C 1s photoemission spectrum of methoxy (CH3O) chemisorbed on Cu(100) is demonstrated to contain a resolvable fine structure due to excitation of the molecular C-H normal vibrational mode. The origin of the fine structure is ascertained by substituting hydrogen with deuterium in the methoxy overlayers and by comparison to gas-phase C 1s spectra for methanol (CH3OH). The vibrational fine structure is demonstrated to provide a fingerprint of the hydrocarbon group present on the surface.

Adsorption sites in O and CO coadsorption phases on Rh(111) investigated by high-resolution core-level photoemission

High-resolution core-level spectroscopy is used in combination with low-energy electron diffraction (LEED) and photoelectron diffraction to identify the adsorption sites for three different coadsorbed phases consisting of ordered overlayers of oxygen coadsorbed with CO on the Rh(111) single-crystal surface. The three ordered overlayer structures, which may be denoted as 2O + CO/Rh(111), O + CO/Rh(111) and O+2CO/Rh(111), all show (2 × 2) LEED patterns. In the 2O + CO and O + CO phases the CO molecules are found to occupy only on-top sites while the O + 2CO phase shows CO molecules in both on-top and three-fold hollow sites. In all cases the oxygen atoms are found in three-fold hollow sites. For the O + CO and O + 2CO phases our results confirm previous determinations by LEED, while the 2O + CO phase has not been observed before on Rh(111). The core-level binding energies of the C 1s and O 1s core levels for both adsorbates are characteristics of the adsorption site and are very close to the binding energies found for the pure cases of only oxygen or CO adsorbed on Rh(111). In the coadsorption phases we find that the interaction between the adsorbates has only a minor influence on the core-level binding energies. For the O + 2CO/Rh(111) coadsorption phase we find that a full CO coverage is not obtained; less than 80% of the unit cells contain two CO molecules, in line with previous findings. (Less)

Adsorption of acetylene and hydrogen on Pd(111): Formation of a well-ordered ethylidyne overlayer

Adsorption of acetylene and hydrogen on Pd(111): Formation of a well-ordered ethylidyne overlayer

Determination of NO adsorption sites on Pd(100) using core level photoemission and low energy electron diffraction

The adsorption of NO on Pd(1 0 0) is investigated with high resolution core level spectroscopy and low energy electron diffraction (LEED). Several ordered NO overlayers were observed, in agreement with earlier Studies. Our data clearly show that NO adsorbs in fourfold hollow sites at coverages tip to 0.25 -0.30 monolayer (ML) whereas at 0.5 ML only bridge sites are occupied. By a reinterpretation of previous electron energy loss spectroscopy (EELS) investigations we show that the new site assignments are in agreement the EELS data, Based on the photoemission results for the N 1s and the Pd 3d core levels we propose new structure models for the (2root2 x 2root2)R45degrees and the p(4 x 2) LEED patterns found at coverages of 0.5 and 0.25 ML, respectively. In the latter case, it is suggested that the p(4 x 2) LEED pattern is formed from domains having p(2 x 2)-NO and c(4 x 2)-2NO unit cells.

Adsorption properties of a mixed surface studied by high resolution core level photoemission : CO/0.5 ML Pd/Rh(111)

The coverage-dependent adsorption properties of a laterally heterogeneous bimetallic surface have been investigated by high resolution core level photoemission and low energy electron diffraction. The specific system under study was CO adsorbed on a Rh(111) surface onto which 2D Pd islands (coverage 0.5 ML) were formed by vapor deposition. The CO adsorption properties of the heterogeneous surface were compared with CO adsorption on a Rh(111) surface covered with a full Pd monolayer and with previous results for the CO/Rh(111) system. For low exposures CO is only found on the Rh(111) patches which can be explained by diffusion of CO from the Pd islands onto Rh parts in the adsorption process. At higher exposures CO diffusion from Rh to Pd is indicated. The origin of the diffusion processes can be found in the different coverage-dependent CO adsorption energies on the two surface parts.

Adsorption sites in coadsorption systems determined by photoemission spectroscopy: K and CO coadsorbed on Rh(111)

The adsorption sites of coadsorbed K and CO on the Rh(111) surface have been determined using high-resolution core-level spectroscopy, low-energy electron diffraction and site-resolved photoelectron diffraction. For both a (2 × 2)-2CO-1K and a (2√3 × 2√3)-6CO-1K structure, we find that the CO molecules occupy threefold hollow sites and the K atoms on-top sites, contrary to the adsorption sites of K (threefold hollow site) and CO (on-top site below 0.5 monolayers) if adsorbed alone on Rh(111). Deposition of K onto a CO precovered surface is found to induce large shifts towards lower binding energy of the C and O 1s core levels (∼0.7 eV for C 1s and ∼1.5 eV for O 1s). The major part of these shifts is shown to arise from the K-induced site change of the CO molecules. This finding may be of importance in the interpretation of XPS data of related co-adsorption systems. Finally, it is suggested that the C and O 1s binding energies provide useful fingerprints of the CO adsorption site also for co-adsorption systems.

Surface chemistry of TiCl4 on clean and hydrogen modified W(110): identification of surface intermediates

The adsorption and decomposition of titanium tetrachloride (TiCl4) on W(110) were studied with high-resolution core level photoelectron spectroscopy. At least two stable intermediates are formed along the pathway to TiCl4 decomposition: TiCl4(a), which is stable up to 300 K, and TiCl3(a), which is stable up to 500 K. Successive adsorption at 80 K shows that the TiCl4() species forms in the presence of dissociated TiCl4 or hydrogen. This indicates that dissociative sites must be blocked before TiCl4 can adsorb intact.

The influence of preadsorbed oxygen on the adsorption of CO on two-dimensional Pd islands on a Rh(111) surface

The influence of preadsorbed oxygen on the CO adsorption properties of a laterally heterogeneous bimetallic surface consisting of Pd islands on Rh(111) at a Pd coverage of 0.5 monolayers has been studied by high resolution core level photoemission. A surface consisting of clean Pd islands surrounded by oxygen-covered Rh(111) patches was prepared by predosing oxygen at room temperature. By applying core level photoemission to the Pd 3d5/2 and the C 1s levels, the adsorption of CO on this surface was studied with particular attention being paid to possible CO diffusion between the two surface parts. The CO molecules are found to diffuse from the oxygen-covered Rh(111) patches onto the Pd islands for low to medium CO exposures. This diffusion direction is opposite of that found previously for the 0.5 ML Pd on Rh(111) system with no oxygen predosing. This reversal of the diffusion direction is argued to be due to a large reduction of the CO adsorption energy on the Rh patches of the surface caused by the preadsorbed oxygen.

Mn-induced NO dissociation on Pd(100)

The changes in the NO adsorption properties of Pd(1 0 0) due to the addition of Mn have been investigated using high resolution core level photoelectron spectroscopy. The Pd(1 0 0) surface was modified by forming a c(2 x 2)-PdMn surface alloy at two different Mn coverages, giving surfaces partly and fully alloyed, respectively, as shown by scanning tunneling microscopy. NO adsorption on the alloy films was found to destroy the c(2 x 2) structure. Dissociation of the NO molecules upon heating is observed, in stark contrast to NO on the clean Pd(1 0 0) surface from which all the molecules desorb intact upon heating. The dissociation process on the c(2 x 2)-PdMn-(1 x 1)-Pd mixed surface is completed at a significantly higher temperature than for the homogeneous c(2 x 2) surface. It is suggested that Mn atoms give rise to NO dissociation at lower temperatures. whereas Pd atoms situated at c(2 x 2)-(1 x 1) boundaries are responsible for the NO decomposition at higher temperatures.

Identification of a laterally mobile state during CO adsorption

We have investigated CO adsorption at 300 K on ~1.5 atomic layer thick Pd films on a Mo(110) surface by high-resolution core level photoemission. We describe how high-resolution core level spectroscopy may be utilized to study the influence of laterally mobile states on the sticking probability of molecules on such a laterally heterogeneous surface. The present Pd films are laterally heterogeneous in the sense that the additional ~0.5 atomic Pd layer forms mesoscopic one-layer thick islands on top of the first Pd layer. At 300 K, CO chemisorbs on these two-layer thick islands but not on the one-layer parts of the film. The rate at which these two-layer islands are filled by CO molecules as the surface is exposed to CO is found to be consistent with a picture where CO molecules that initially impinge on the one-layer parts of the surface enter a laterally mobile state and diffuse to the two-layer islands and adsorb there. This mobile state is in many respects similar to a classical precursor state.