Morphological modifications of Ag/Cu(111) probed by photoemission spectroscopy of quantum well states and the Shockley surface state

Epitaxial ultra-thin Ag films grown on Cu(111) have been investigated by angle-resolved photoemission spectroscopy. The thickness dependence of the binding energy for the Shockley surface state at 300 K could be determined accurately in films up to 5 ML thick. Furthermore, we observe drastic changes in the film morphology after annealing to 450 K. Spectral modifications in the shape of the quantum-well states (QWS), characteristic for these ultra-thin silver films, prove that the surface morphology is homogeneous. The photoemission spectra also indicate that the silver film bifurcates to form a film exhibiting two distinct film thicknesses. For all levels of silver coverage, we identify surface regions that are 2 ML thick, while the thickness of the remaining surface depends on the amount of deposited silver. The almost purely Lorentzian line-shape of the spectral features corresponding to the two different surface regions show that both surface areas are atomically flat. PACS 68.55.Jk; 73.20.At; 73.21.Fg; 79.60.Dp     

Numerical simulation of the effect of grain fragmentation on the evolution of microstructure quantities

Meccanica - In this paper the effect of grain fragmentation of a cohesionless granular material on the change of microstructure quantities is investigated using a micropolar continuum model. To...     

Electronic Transitions in Different Redox States of Trinuclear 5,6,11,12,17,18-Hexaazatrinaphthylene-Bridged Titanium Complexes: Spectroelectrochemistry and Quantum Chemistry

Multinuclear transition metal complexes bridged by ligands with extended π-electronic systems show a variety of complex electronic transitions and electron transfer reactions. While a systematic understanding of the photochemistry and electrochemistry has been attained for binuclear complexes, much less is known about trinuclear complexes such as hexaphenyl-5,6,11,12,17,18-hexaazatrinaphthylene-tristitanocene [(Cp₂Ti)₃HATN(Ph)₆]. The voltammogram of [(Cp₂Ti)₃HATN(Ph)₆] shows six oxidation and three reduction waves. Solution spectra of [(Cp₂Ti)₃HATN(Ph)₆] and of the electrochemically formed oxidation products show electronic transitions in the UV, visible and the NIR ranges. Density functional theory (DFT) and linear response time-dependent DFT show that the three formally titanium(II) centers transfer an electron to the HATN ligand in the ground state. The optically excited transitions occur exclusively between ligand-centered orbitals. The charged titanium centers only provide an electrostatic frame to the extended π-electronic system. Complete active self-consistent field (CASSCF) calculation on a structurally simplified model compound, which considers the multi-reference character imposed by the three titanium centers, can provide an interpretation of the experimentally observed temperature-dependent magnetic behavior of the different redox states of the title compound in full consistency with the interpretation of the electronic spectra.     

Thermal desorption of metals from tungsten single crystal surfaces

After a short review of the experimental methods used to determine desorption energies E and frequencies v the assumptions underlying the theoretical analysis of the experimental data are discussed. Then recent experimental results on the flash desorption of Cu, Ag and Au from clean, well characterized W {110} and {100} surfaces are presented and analysed in detail, in particular with respect to the coverage dependence. The results obtained this way clearly reveal the limitations of previous analysis methods and of the experimental technique per se (such as structure and phase changes below and in the temperature region in which desorption occurs). Furthermore the need for more theoretical work to understand the large changes of v and E with coverage and the so-called “compensation effect”, i.e. the relation between In v and E, becomes evident.     

Sintering of a bcc structure of spherical particles of equal and different sizes

Solid-state sintering of a bcc structure of spherical particles has been studied numerically by use of simple shape parameters to describe the state of the unit cell. Both free and pressure-assisted sintering of particles of equal and different sizes for various ratios of boundary and surface diffusion have been considered. At low relative densities, the evolution of particle radius, interparticle junction radius and shrinkage predicted by the bcc model are rather similar to sintering of a simple row of particles. At higher densities, the porosity closes up; that is, the junctions start to interact, or the next-nearest neighbours in the particle structure attain contact. Quantative measures of the density at the transition from open pore space between the particles to closed porosity as well as the density at which the next-nearest neighbours start to touch are derived. Furthermore, different dihedral angles and the evolution of relative density and sintering stresses are studied.     

Toeplitz quantization on Fock space

For Toeplitz operators $T_f^{(t)}$ acting on the weighted Fock space $H_t^2$, we consider the semi-commutator $T_f^{(t)}{T}_g^{(t)}?T_{fg}^{(t)}$, where $t>0$ is a certain weight parameter that may be interpreted as Planck's constant ? in Rieffel's deformation quantization. In particular, we are interested in the semi-classical limit

($?$)$\underset{t\to 0}{\lim }?{6T_f^{(t)}{T}_g^{(t)}?T_{fg}^{(t)}6}_t.$

It is well-known that ${6T_f^{(t)}{T}_g^{(t)}?T_{fg}^{(t)}6}_t$ tends to 0 under certain smoothness assumptions imposed on f and g. This result was recently extended to $f,g\in \mathrm{BUC}({\mathbb{C}}^n)$ by Bauer and Coburn. We now further generalize (?) to (not necessarily bounded) uniformly continuous functions and symbols in the algebra $\mathrm{VMO}\cap L^{\infty }$ of bounded functions having vanishing mean oscillation on ${\mathbb{C}}^n$. Our approach is based on the algebraic identity $T_f^{(t)}{T}_g^{(t)}?T_{fg}^{(t)}=?{(H_{\overline{f}}^{(t)})}^{?}{H}_g^{(t)}$, where $H_g^{(t)}$ denotes the Hankel operator corresponding to the symbol g, and norm estimates in terms of the (weighted) heat transform. As a consequence, only f (or likewise only g) has to be contained in one of the above classes for (?) to vanish. For g we only have to impose ${\lim \sup }_{t\to 0}{6H_g^{(t)}6}_t<\infty$, e.g. $g\in L^{\infty }({\mathbb{C}}^n)$. We prove that the set of all symbols $f\in L^{\infty }({\mathbb{C}}^n)$ with the property that ${\lim }_{t\to 0}?{6T_f^{(t)}{T}_g^{(t)}?T_{fg}^{(t)}6}_t={\lim }_{t\to 0}?{6T_g^{(t)}{T}_f^{(t)}?T_{gf}^{(t)}6}_t=0$ for all $g\in L^{\infty }({\mathbb{C}}^n)$ coincides with $\mathrm{VMO}\cap L^{\infty }$. Additionally, we show that $\underset{t\to 0}{\lim }?{6T_f^{(t)}6}_t={6f6}_{\infty }$ holds for all $f\in L^{\infty }({\mathbb{C}}^n)$. Finally, we present new examples, including bounded smooth functions, where (?) does not vanish.     

Tetraammine(selenito‐O,O′)cobaltate(III) nitrate monohydrate

The title compound crystallizes as the mono­hydrate, [Co(SeO₃)(NH₃)₄]NO₃·H₂O. The crystallographic mirror symmetry coincides with the molecular symmetry; the mirror plane passes through the cation, anion and water mol­ecule. The CoN₄O₂ octahedron is distorted, with the selenito group acting as a bidentate ligand through two bridging O atoms to the cobalt. The coordinated Se—O distance is 1.742 (2) Å, whereas the uncoordinated Se—O distance is 1.646 (3) Å. A three‐dimensional hydrogen‐bonded network exists between [Co(SeO₃)(NH₃)₄]NO₃ and the water mol­ecule. The nitrate anion and water mol­ecule form open pores in the structure when hydrogen bonded to two neighboring [Co(SeO₃)(NH₃)₄]⁺ cations. Selenium participates in two types of relatively close intermolecular interactions with neighboring charged species (Se?N1 and Se?O3), but does not participate in an interaction with a neighboring O2 atom, the nearest contact distance being 4.638 (3) Å.