The adsorption structure of furan on Pd(1 1 1)

The structure of molecular furan, C4H4O, on Pd(1 1 1) has been investigated by O K-edge near-edge X-ray absorption fine structure (NEXAFS) and C 1s scanned-energy mode photoelectron diffraction (PhD). NEXAFS shows the molecule to be adsorbed with the molecular plane close to parallel to the surface, a conclusion confirmed by the PhD analysis. Chemical-state specific C 1s PhD data were obtained for the two inequivalent C atoms in the furan, the α-C atoms adjacent to the O atom, and the β-C atoms bonded only to C atoms, but only the PhD modulations for the α-C emitters were of sufficiently large amplitude for detailed evaluation using multiple scattering calculations. This analysis shows the α-C atoms to be located approximately 0.6 Å off-atop surface Pd atoms with an associated C–Pd bondlength of 2.13 ± 0.03 Å. Two alternative local geometries consistent with the data place the O atom in off-atop or near-hollow locations, and for each of these local structures there are two equally-possible registries relative to the fcc and hcp hollow sites. The results are in good agreement with earlier density functional theory calculations which indicate that the fcc and hcp registries are equally probable, but the PhD results fail to distinguish the two distinct local bonding geometries

A structural study of a C3H3 species coadsorbed with CO on Pd(1 1 1)

The combination of chemical-state-specific C 1s scanned-energy mode photoelectron diffraction (PhD) and O K-edge near-edge X-ray absorption fine structure (NEXAFS) has been used to determine the local adsorption geometry of the coadsorbed C3H3 and CO species formed on Pd(1 1 1) by dissociation of molecular furan. CO is found to adopt the same geometry as in the Pd(1 1 1)c(4 × 2)-CO phase, occupying the two inequivalent three-fold coordinated hollow sites with the C–O axis perpendicular to the surface. C3H3 is found to lie with its molecular plane almost parallel to the surface, most probably with the two ‘outer’ C atoms in equivalent off-atop sites, although the PhD analysis formally fails to distinguish between two distinct local adsorption sites

Solid solution hardening of vacancy stabilized TixW1−xB2

AbstractWe present a combined experimental and theoretical investigation of sputter deposited thin films in the ternary system Ti1−xWxB2. Solid solutions of Ti1−xWxB2−z were prepared by physical vapor deposition (PVD) and, over the whole composition range, found to crystallize in the AlB2 structure type. The obtained films exhibit good thermal stability and high hardness, evidencing a maximum value of almost 40GPa for Ti0.67W0.33B2−z. The effect of vacancies on stabilization and mechanical properties of the AlB2 structure type is discussed, using ab initio simulations. Based on our results, we can conclude that vacancies are crucial for the phase stability of PVD deposited Ti1−xWxB2−z coatings

The local adsorption structure of benzene on Si(001)-(2 × 1): a photoelectron diffraction investigation

Scanned-energy mode C 1s photoelectron diffraction has been used to investigate the local adsorption geometry of benzene on Si(001) at saturation coverage and room temperature. The results show that two different local bonding geometries coexist, namely the 'standard butterfly' (SB) and 'tilted bridge' (TB) forms, with a composition of 58 ± 29% of the SB species. Detailed structural parameter values are presented for both species including Si–C bond lengths. On the basis of published measurements of the rate of conversion of the SB to the TB form on this surface, we estimate that the timescale of our experiment is sufficient for achieving equilibrium, and in this case our results indicate that the difference in the Gibbs free energy of adsorption, ΔG(TB)−ΔG(SB), is in the range −0.023 to +0.049 eV. We suggest, however, that the relative concentration of the two species may also be influenced by a combination of steric effects influencing the kinetics, and a sensitivity of the adsorption energies of the adsorbed SB and TB forms to the nature of the surrounding benzene molecules

Photoelectron diffraction investigation of the structure of the clean TiO2(110)(1×1) surface

The surface relaxations of the rutile TiO2(110)(1×1) clean surface have been determined by O 1 s and Ti 2p3∕2 scanned-energy mode photoelectron diffraction. The results are in excellent agreement with recent low-energy electron diffraction (LEED) and medium energy ion scattering (MEIS) results, but in conflict with the results of some earlier investigations including one by surface x-ray diffraction. In particular, the bridging O atoms at the surface are found to relax outward, rather than inward, relative to the underlying bulk. Combined with the recent LEED and MEIS results, a consistent picture of the structure of this surface is provided. While the results of the most recent theoretical total-energy calculations are qualitatively consistent with this experimental consensus, significant quantitative differences remain

Local adsorption geometry of acetylene on Si(100)(2×1)

Using C 1s scanned-energy-mode photoelectron diffraction the local adsorption geometry of acetylene on the Si(100)(2x1) surface has been determined and the results are compared with those of a similar study of ethylene adsorption on this surface. Both molecules bond to the surface along the Si-Si dimers with the C-C bonds parallel to the surface such that the C atoms are in off-atop sites relative to the Si dimer atoms. In both cases the Si-Si bond length (2.36±0.21 Å for ethylene and 2.44±0.58 Å for acetylene) is compatible only with the dimer remaining intact after adsorption and not with the Si-Si distance of an ideally terminated undimerized Si(100) surface (3.84 Å)

Adsorption site and orientation of pyridine on Cu{110} determined by photoelectron diffraction

The local adsorption geometry of pyridine on Cu{110} has been determined quantitatively using photoelectron diffraction in the scanned-energy mode. At high coverages the molecule adsorbs nearly atop a Cu atom in the close-packed rows with a N–Cu bond length of 2.00 Å. Moreover, the Cu–N axis and the molecular (C2) axis are inclined by 8° and 20°, respectively, to the surface normal. The result shows that not only the adsorption site of the emitter (in this case the N atom) but also the position of relatively light scatterers (the C atoms) can be determined by photoelectron diffraction

Photoelectron diffraction: from phenomenological demonstration to practical tool

The potential of photoelectron diffraction—exploiting the coherent interference of directly-emitted and elastically scattered components of the photoelectron wavefield emitted from a core level of a surface atom to obtain structural information—was first appreciated in the 1970s. The first demonstrations of the effect were published towards the end of that decade, but the method has now entered the mainstream armoury of surface structure determination. This short review has two objectives: First, to outline the way that the idea emerged and the way this evolved in my own collaboration with Neville Smith and his colleagues at Bell Labs in the early years: Second, to provide some insight into the current state-of-the art in application of (scanned-energy mode) photoelectron diffraction to address two key issue in quantitative surface structure determination, namely, complexity and precision. In this regard a particularly powerful aspect of photoelectron diffraction is its elemental and chemical-state specificity