Experiments in a rotating Hele-Shaw cell

We introduce a modification to Hele-Shaw flows consisting of a rotating cell. A viscous fluid (oil) is injected at the rotation axis of the cell, which is open to air. The morphological instability of the oil-air interface is thus driven by centrifugal force and is controlled by the density (not viscosity) difference. We derive the linear dispersion relation and verify the maximum growth rate selection of initial patterns within experimental uncertainty. The nonlinear growth regime is studied in the case of vanishing injection rate. Several characteristic lengths are studied to quantify the patterns obtained. Experimental data exhibit good collapse for two characteristic lengths, namely, the radius of gyration and the radial finger length, which in the nonlinear regime appear to grow linearly in time.

Influence of hydrodynamic interactions on the adsoption process of large particles

We have studied the adsorption process of non-Brownian particles on a line. Our work differs from previously proposed models in that we have incorporated hydrodynamic interactions between the incoming particles and the preadsorbed particles as well as the surface. We then numerically analyze the effect of these interactions on quantities related to the adsorption process. Comparing our model to the ballistic deposition model (BM) shows a significant discrepancy in the pair correlation function. These results can explain some differences between recent experiments and BM predictions. Finally, the limitations of the applicability of BM are addressed.

Adsorption kinetics in the presence of external fields

In this article we present a detailed analysis of the kinetics of a class of sequential adsorption models that take into account the effect of externally applied fields (as an electric field, or a shear rate) on the adsorption. The excluded volume interactions related to the finite size of the adsorbing particles are modified by the external fields. As a result, new adsorption mechanisms appear with respect to the ones used to describe the kinetics in a quiescent fluid. In particular, if the adsorbing particles are allowed to roll over preadsorbed ones, adsorption becomes non local even in the simplest geometry. An exact analytic theory cannot be developed, but we introduce a self-consistent theory that turns out to agree with the simulation results over all the range of the parameters.

Influence of an inert electrolyte on the morphology of quasi-two-dimensional electrodeposits

The influence of an inert electrolyte (sodium sulfate) on quasi-two-dimensional copper electrodeposition from a nondeaerated aqueous copper sulfate solution has been analyzed. The different morphologies for a fixed concentration of CuSO4 have been classified in a diagram in terms of the applied potential and the inert electrolyte concentration. The main conclusion is the extension of the well-known Ohmic model for the homogeneous growth regime for copper sulfate solutions with small amounts of sodium sulfate. Moreover, we have observed the formation of fingerlike deposits at large applied potential and inert electrolyte concentration values, before hydrogen evolution becomes the main electrode reaction.

Chemisorption of atomic aluminum on Si(111): Evidence for an adsorbate-induced relaxation based on ab initio cluster-model calculations

Interaction models of atomic Al with Si4H9, Si4H7, and Si6H9 clusters have been studied to simulate Al chemisorption on the Si(111) surface in the atop, fourfold atop, and open sites. Calculations were carried out using nonempirical pseudopotentials in the framework of the ab initio Hartree-Fock procedure. Equilibrium bond distances, binding energies for adsorption, and vibrational frequencies of the adatoms are calculated. Several basis sets were used in order to show the importance of polarization effects, especially in the binding energies. Final results show the importance of considering adatom-induced relaxation effects to specify the order of energy stabilities for the three different sites, the fourfold atop site being the preferred one, in agreement with experimental findings.

Ab initio cluster-model study of the on-top chemisorption of F and Cl on Si(111) and Ge(111) surfaces

The interaction of atomic F and Cl with Si4H9 and Ge4H9 cluster models has been studied by using ab initio pseudopotentials and basis sets of increasing complexity. The results show that the effect of d orbitals is important in order to reproduce the experimental findings. However, the use of polarization functions in the atoms which are directly involved in the chemisorption bond leads to results which are very close to those obtained using extended basis sets. The local nature of the chemisorption bond is also interpreted by means of a Mulliken population analysis. For F-Si4H9 and Cl-Si4H9 the present results are in good agreement with previous ab initio all-electron calculations, and for the chemisorption of Cl on Si(111) and Ge(111) surfaces, good agreement is found with respect to the available experimental results as well as with previous slab calculations based on the local-density-functional formalism.

Chemisorption of group-III metals on the Si(111) and Ge(111) surfaces: An ab initio study

Chemisorption of group-III metal adatoms on Si(111) and Ge(111) has been studied through the ab initio Hartree-Fock method including nonempirical pseudopotentials and using cluster models to simulate the surface. Three different high-symmetry sites (atop, eclipsed, and open) have been considered by using X4H9, X4H7, and X6H9 (X=Si,Ge) cluster models. In a first step, ideal surface geometries have been used. Metal-induced reconstruction upon chemisorption has also been taken into account. Equilibrium distances, binding energies, and vibrational frequencies have been obtained and compared with available experimental data. From binding-energy considerations, the atop and eclipsed sites seem to be the most favorable ones and thus a coadsorption picture may be suggested. Group-III metals exhibit a similar behavior and the same is true for Si(111) and Ge(111) surfaces when chemisorption is considered.

Evidence for two different bonding mechanisms of Al on Si(111)

By means of the ab initio cluster-model approach, we present theoretical evidence for two different mechanisms of bonding of atomic Al to Si(111). On the atop site (T1) the interaction of atomic Al to Si(111) is characteristic of an ionic bond whereas interaction above the threefold eclipsed site (T4) leads to the formation of a typical covalent bond. Moreover, both sites have a similar interaction energy if electronic correlation effects are included. While the conclusions regarding the nature of the chemisorption bond in the two sites do not depend either on the cluster-model size, the kind of embedding hydrogen atoms used, or the quality of the wave function (Hartree-Fock or configuration interaction), the chemisorption energy depends strongly on the wave function used. In fact, inclusion of correlation energy is necessary to properly describe the interaction energies.

Ground and excited states of KNiF3: An ab initio cluster-model approach

Finite cluster models and a variety of ab initio wave functions have been used to study the electronic structure of bulk KNiF3. Several electronic states, including the ground state and some charge-transfer excited states, have been considered. The study of the cluster-model wave functions has permitted an understanding of the nature of the chemical bond in the electronic ground state. This is found to be highly ionic and the different ionic and covalent contributions to the bonding have been identified and quantified. Finally, we have studied the charge-transfer excited states leading to the optical gap and have found that calculated and experimental values are in good agreement. The wave functions corresponding to these excited states have also been analyzed and show that although KNiF3 may be described as a ligand-to-metal charge-transfer insulator there is a strong configuration mixing with the metal-to-metal charge-transfer states.

Rigorous characterization of oxygen vacancies in ionic oxides

Charged and neutral oxygen vacancies in the bulk and on perfect and defective surfaces of MgO are characterized as quantum-mechanical subsystems chemically bonded to the host lattice and containing most of the charge left by the removed oxygens. Attractors of the electron density appear inside the vacancy, a necessary condition for the existence of a subsystem according to the atoms in molecules theory. The analysis of the electron localization function also shows attractors at the vacancy sites, which are associated to a localization basin shared with the valence domain of the nearest oxygens. This polyatomic superanion exhibits chemical trends guided by the formal charge and the coordination of the vacancy. The topological approach is shown to be essential to understand and predict the nature and chemical reactivity of these objects. There is not a vacancy but a coreless pseudoanion that behaves as an activated host oxygen.

Alignment of hexatic langmuir monolayers under shear

We have studied the structural changes that fatty acid monolayers in the Ov phase undergo when a simple shear flow is imposed. A strong coupling is revealed by the changes in domain structure that are observable using Brewster angle microscopy, suggesting the possibility of shear alignment. The dependence of the alignment on the molecular polar tilt proves that the mechanism is different than in nematic liquid crystals. We argue that the degenerate lattice symmetry lines of the underlying pseudohexagonal lattice align in the flow direction, and we explain the observed alignment angle using geometrical arguments.

Constitutive activity of receptors coupled to guanine nucleotide regulatory proteins.

Adrenoceptors are prototypic members of the superfamily of seven transmembrane domain, G protein-coupled receptors. Study of the properties of several mutationally activated adrenoceptors is deepening understanding of the normal functioning of this ubiquitous class of receptors. The new findings suggest an expansion of the classical ternary complex model of receptor action to include an explicit isomerization of the receptors from an inactive to an active state which couples to the G protein ('allosteric ternary complex model'). This isomerization involves conformational changes which may occur spontaneously, or be induced by agonists or appropriate mutations which abrogate the normal 'constraining' function of the receptor, allowing it to 'relax' into the active conformation. Robert Lefkowitz and colleagues discuss the physiological and pathophysiological implications of these new insights into regulation of receptor activity.

Sellun kuivauskoneen ajettavuusongelman monimuuttujainen tarkastelu

Tässä työssä on tutkittu sellun kuivauskoneella koivusellua kuivattaessa esiintyvää ajettavuusongelmaa. Tähän ongelmaan on etsitty ratkaisua monimuuttujamenetelmien avulla. Työn kirjallisuusosassa on lyhyesti käyty läpi sellun kuivauskoneiden historia lieriöviirakoneista nykyaikaisiin kaksoisviirasovelluksiin. Lisäksi kirjallisuusosassa on käsitelty tässä työssä käytettyjen monimuuttujamenetelmien perusteet ja käyty esimerkin omaisesti läpi joitakin kemometrian sovelluksia puunjalostusteollisuudessa. Työn kokeellisessa osassa on haettu tiedonkeruujärjestelmästä massan ominaisuuksista ja kuivauskoneen ajoparametreistä koostuvaa dataa vuoden 1999 ajalta. Tästä datasta on tehty PCA-mallit vuoden 1999 jokaisen kuukauden datasta ja diskriminoiva PLS-malli ajettavuuden kannalta hyvästä ja huonosta jaksosta koostuvasta datasta. Kuivauskoneelta on koottu dataa myös ottamalla kiertovesi- ja selluarkkinäytteitä. Kiertovesinäytteiden analyysituloksista on tehty PCA-mallit ja lisäksi analyysitulokset on tarkasteltu yksimuuttujaisesti. Selluarkkinäytteistä on määritetty UV-spektrit ja niistä on tehty PCA-mallit, jotta spektreistä saataisiin mahdollisimman paljon informaatiota. Työssä on havaittu yhdeksi selitykseksi ajettavuusongelmalle kuivauskoneen kiertovesien likaantuminen. Kiertovesiä ja massarainan pintakemiaa tulisi kuitenkin tutkia laajemmassa mittakaavassa kuin tämän työn puitteissa on ollut mahdollista tutkia.