A monopole mass filter with a hyperbolic V-shaped electrode

In this article we compare the classical monopole mass filter of von Zahn and the monopole mass filter with a hyperbolic V-shaped electrode. The experimental results and those of computer simulation for both mass spectrometers are presented. We show that the replacement of a conventional 90 degrees V-shaped electrode by an electrode with a hyperbolic profile substantially improves the peak shape of any given mass, and increases the mass resolution by a factor of 3-4 and the abundance sensitivity by a factor of 100. The potential of high analytical performance combined with electroforming techniques for electrode manufacture indicate future practical uses of such instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Vanadium oxides on aluminum oxide supports. 2. Structure, vibrational properties, and reducibility of V2O5 clusters on alpha-Al2O3(0001)

The structure, stability, and vibrational properties of isolated V2O5 clusters on the Al2O3(0001) surface have been studied by density functional theory and statistical thermodynamics. The most stable structure does not possess vanadyl oxygen atoms. The positions of the oxygen atoms are in registry with those of the alumina support, and both vanadium atoms occupy octahedral sites. Another structure with one vanadyl oxygen atom is only 0.12 eV less stable. Infrared spectra are calculated for the two structures. The highest frequency at 922 cm(-1) belongs to a V-O stretch in the V-O-Al interface bonds, which supports the assignment of such a mode to the band observed around 941 cm(-1) for vanadia particles on alumina. Removal of a bridging oxygen atom from the most stable cluster at the V-O-Al interface bond costs 2.79 eV. Removal of a (vanadyl) oxygen atom from a thin vanadia film on alpha-Al2O3 costs 1.3 eV more, but removal from a V2O5(001) single-crystal surface costs 0.9 eV less. Similar to the V2O5(001) surface, the facile reduction is due to substantial structure relaxations that involve formation of an additional V-O-V bond and yield a pair of V(IV)(d1) sites instead of a V(III)(d2)/V(V)(d0) pair.     

The structure of epitaxial V2O3 films and their surfaces: A medium energy ion scattering study

Medium energy ion scattering, using 100 keV H⁺ incident ions, has been used to investigate the growth of epitaxial films, up to thicknesses of ~ 200 Å, of V₂O₃ on both Pd(111) and Au(111). Scattered-ion energy spectra provide a measure of the average film thickness and the variations in this thickness, and show that, with suitable annealing, the crystalline quality is good. Plots of the scattering yield as a function of scattering angle, so-called blocking curves, have been measured for two different incidence directions and have been used to determine the surface structure. Specifically, scattering simulations for a range of different model structures show poor agreement with experiment for half-metal (….V′O₃V) and vanadyl (….V′O₃V=O) terminations, with and without surface interlayer relaxations. However, good agreement with experiment is found for the modified oxygen-termination structure, first proposed by Kresse et al., in which a subsurface V half-metal layer is moved up into the outermost V buckled metal layer to produce a VO₂ overlayer on the underlying V₂O₃, with an associated layer structure of ….O₃VV′′V ′O₃. This result is consistent with the predictions of thermodynamic equilibrium at the surface under the surface preparation conditions, but is at variance with the conclusions of earlier studies of this system that have favoured the vanadyl termination. The results of these previous studies are re-evaluated in the light of the new result.     

Counting electrons transferred through a thin alumina film into Au chains

Low-temperature STM measurements combined with density functional theory calculations are employed to study the adsorption of gold on alumina/NiAl(110). The binding of Au monomers involves breaking of an oxide Al-O bond below the adatom and stabilizing the hence undercoordinated O ion by forming a new bond to an Al atom in the NiAl. The adsorption implies negative charging of the adatom. The linear arrangement of favorable binding sites induces the self-organization of Au atoms into chains. For every ad-chain, the number of transfer electrons from the support is determined by analyzing the node structure of the corresponding highest occupied molecular orbital.     

Local canted spin behaviour in Co1.4−x Zn x Ge0.4Fe1.2O4 spinels: A macroscopic, mesoscopic and microscopic study

DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements have been reported for the Co_1.1−x Zn _x Ge_0.1Fe_1.2O₁ spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important role of magnetic anisotropy (due to the presence of Co²⁺ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed.     

Catalysis and corrosion: the theoretical surface-science context

Numerous experiments in ultra-high vacuum as well as (T=0 K, p=0) theoretical studies on surfaces have been performed over the last decades in order to gain a better understanding of the mechanisms, which, for example, underlie the phenomena of catalysis and corrosion. Often the results achieved this way cannot be extrapolated directly to the technologically relevant situation of finite temperature and high pressure. Accordingly, modern surface science has realized that bridging the so-called pressure gap (getting out of the vacuum) is the inevitable way to go. Of similar importance are studies in which the temperature is changed systematically (warming up and cooling down). Both aspects are being taken into account in recent experiments and ab initio calculations.

In this paper we stress that there is still much to learn and important questions to be answered concerning the complex atomic and molecular processes which occur at surfaces and actuate catalysis and corrosion, although significant advances in this exciting field have been made over the years. We demonstrate how synergetic effects between theory and experiment are leading to the next step, which is the development of simple concepts and understanding of the different modes of the interaction of chemisorbed species with surfaces. To a large extent this is being made possible by recent developments in theoretical methodology, which allow to extend the ab initio (i.e., starting from the self-consistent electronic structure) approach to poly-atomic complexes with 10,000 and more atoms, time scales of seconds, and involved statistics (e.g., ab initio molecular dynamics with 10,000 and more trajectories). In this paper we will

1. sketch recent density–functional theory based hybrid methods, which bridge the length and time scales from those of electron orbitals to meso- and macroscopic proportions, and

2. present some key results on properties of surfaces, demonstrating their role in corrosion and heterogeneous catalysis. In particular we discuss

◦ the influence of the ambient gas phase on the surface structure and stoichiometry,

◦ adsorbate phase transitions and thermal desorption, and

◦ the role of atoms' dynamics and statistics for the surface chemical reactivity.