Plane waves in noncommutative fluids

We study the dynamics of the noncommutative fluid in the Snyder space perturbatively at the first order in powers of the noncommutative parameter. The linearized noncommutative fluid dynamics is described by a system of coupled linear partial differential equations in which the variables are the fluid density and the fluid potentials. We show that these equations admit a set of solutions that are monochromatic plane waves for the fluid density and two of the potentials and a linear function for the third potential. The energy-momentum tensor of the plane waves is calculated. © 2013 Elsevier B.V.

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Charge dynamics in half-filled Hubbard chains with finite on-site interaction

We study the charge dynamic structure factor of the one-dimensional Hubbard model with finite on-site repulsion U at half-filling. Numerical results from the time-dependent density matrix renormalization group are analyzed by comparison with the exact spectrum of the model. The evolution of the line shape as a function of U is explained in terms of a relative transfer of spectral weight between the two-holon continuum that dominates in the limit U -> infinity and a subset of the two-holon-two-spinon continuum that reconstructs the electron-hole continuum in the limit U -> 0. Power-law singularities along boundary lines of the spectrum are described by effective impurity models that are explicitly invariant under spin and eta-spin SU(2) rotations. The Mott-Hubbard metal-insulator transition is reflected in a discontinuous change of the exponents of edge singularities at U = 0. The sharp feature observed in the spectrum for momenta near the zone boundary is attributed to a van Hove singularity that persists as a consequence of integrability.

Magnetic field induced charge redistribution in artificially disordered quantum Hall superlattices

The photoluminescence from individual quantum wells of artificially disordered weakly coupled multi-layers embedded in wide AlGaAs parabolic wells was investigated in a strong magnetic field. We show that the response of the individual wells is very different from the average response of the multi-layers studied by transport measurements and that photoluminescence represents a local probe of the quantum Hall state formed in three-dimensional electron system. The observed magnetic field induced variations of the in-layer electron density demonstrate the formation of a new phase in the quasi-three-dimensional electron system. The sudden change in the local electron density found at the Landau filling factor nu = 1 by both the magneto-transport and the magneto-photoluminescence measurements was assigned to the quantum phase transition. Copyright (C) EPLA, 2012

Laminated Tubular-channel Ferroelectret Systems from Low-density Polyethylene Films and from Fluoroethylene-propylene Copolymer Films - A Comparison

A template-based lamination technique for the manufacture of ferroelectrets from uniform electret films was recently reported. In the present work, this technique is used to prepare similar ferroelectret structures from low-density polyethylene (LDPE) films and from fluoro-ethylene-propylene (FEP) copolymer films. A comparative analysis of the pressure-, temperature-, and frequency-dependent piezoelectric properties has been performed on the two ferroelectret systems. It is observed that the FEP ferroelectrets exhibit better piezoelectric responses and are thermally more stable. The difference between the piezoelectric d(33) coefficients of the two ferroelectret systems is partially explained here by their different elastic moduli. The anti-resonance peaks of both structures have been investigated by means of dielectric resonance spectroscopy and electroacoustic sound-pressure measurements. A difference of more than 10 kHz is observed between the anti-resonance frequencies of the two ferroelectret systems.

Geometrical and kinematic properties of interfacial waves in stratified oil-water flow in inclined pipe

The stratified oil-water flow pattern is common in the petroleum industry, especially in offshore directional wells and pipelines. Previous studies have shown that the phenomenon of flow pattern transition in stratified flow can be related to the interfacial wave structure (problem of hydrodynamic instability). The study of the wavy stratified flow pattern requires the characterization of the interfacial wave properties, i.e., average shape, celerity and geometric properties (amplitude and wavelength) as a function of holdup, inclination angle and phases' relative velocity. However, the data available in the literature on wavy stratified flow is scanty, especially in inclined pipes and when oil is viscous. This paper presents new geometric and kinematic interfacial wave properties as a function of a proposed two-phase Froude number in the wavy-stratified liquid-liquid flow. The experimental work was conducted in a glass test line of 12 m and 0.026 m id., oil (density and viscosity of 828 kg/m(3) and 0.3 Pa s at 20 degrees C, respectively) and water as the working fluids at several inclinations from horizontal (-20 degrees, -10 degrees, 0 degrees, 10 degrees, 20 degrees). The results suggest a physical relation between wave shape and the hydrodynamic stability of the stratified liquid-liquid flow pattern. (C) 2011 Elsevier Inc. All rights reserved.

Study of the Influence of Localized Vibrational Modes in Charge Transport Properties at Nanoscale Systems.

In molecular and atomic devices the interaction between electrons and ionic vibrations has an important role in electronic transport. The electron-phonon coupling can cause the loss of the electron's phase coherence, the opening of new conductance channels and the suppression of purely elastic ones. From the technological viewpoint phonons might restrict the efficiency of electronic devices by energy dissipation, causing heating, power loss and instability. The state of the art in electron transport calculations consists in combining ab initio calculations via Density Functional Theory (DFT) with Non-Equilibrium Green's Function formalism (NEGF). In order to include electron-phonon interactions, one needs in principle to include a self-energy scattering term in the open system Hamiltonian which takes into account the effect of the phonons over the electrons and vice versa. Nevertheless this term could be obtained approximately by perturbative methods. In the First Born Approximation one considers only the first order terms of the electronic Green's function expansion. In the Self-Consistent Born Approximation, the interaction self-energy is calculated with the perturbed electronic Green's function in a self-consistent way. In this work we describe how to incorporate the electron-phonon interaction to the SMEAGOL program (Spin and Molecular Electronics in Atomically Generated Orbital Landscapes), an ab initio code for electronic transport based on the combination of DFT + NEGF. This provides a tool for calculating the transport properties of materials' specific system, particularly in molecular electronics. Preliminary results will be presented, showing the effects produced by considering the electron-phonon interaction in nanoscale devices.

A Galactic ring of minimum stellar density near the solar orbit radius

We analyse the secular effects of a long-lived Galactic spiral structure on the stellar orbits with mean radii close to the corotation resonance. By test-particle simulations and different spiral potential models with parameters constrained on observations, we verified the formation of a minimum with amplitude ∼30–40 per cent of the background disc stellar density at corotation. Such a minimum is formed by the secular angular momentum transfer between stars and the spiral density wave on both sides of corotation. We demonstrate that the secular loss (gain) of angular momentum and decrease (increase) of mean orbital radius of stars just inside (outside) corotation can counterbalance the opposite trend of exchange of angular momentum shown by stars orbiting the librational points L4/5 at the corotation circle. Such secular processes actually allow steady spiral waves to promote radial migration across corotation. We propose some pieces of observational evidence for the minimum stellar density in the Galactic disc, such as its direct relation to the minimum in the observed rotation curve of the Galaxy at the radius r ∼ 9 kpc (for R0 = 7.5 kpc), as well as its association with a minimum in the distribution of Galactic radii of a sample of open clusters older than 1Gyr. The closeness of the solar orbit adius to the corotation resonance implies that the solar orbit lies inside a ring of minimum surface density (stellar + gas). This also implies a correction to larger values for the estimated total mass of the Galactic disc, and consequently, a greater contribution of the disc componente to the inner rotation curve of the Galaxy.

Analysis of charge-transport properties in GST materials for next generation phase-change memory devices

The quest for universal memory is driving the rapid development of memories with superior all-round capabilities in non-volatility, high speed, high endurance and low power. The memory subsystem accounts for a significant cost and power budget of a computer system. Current DRAM-based main memory systems are starting to hit the power and cost limit. To resolve this issue the industry is improving existing technologies such as Flash and exploring new ones. Among those new technologies is the Phase Change Memory (PCM), which overcomes some of the shortcomings of the Flash such as durability and scalability. This alternative non-volatile memory technology, which uses resistance contrast in phase-change materials, offers more density relative to DRAM, and can help to increase main memory capacity of future systems while remaining within the cost and power constraints. Chalcogenide materials can suitably be exploited for manufacturing phase-change memory devices. Charge transport in amorphous chalcogenide-GST used for memory devices is modeled using two contributions: hopping of trapped electrons and motion of band electrons in extended states. Crystalline GST exhibits an almost Ohmic I(V) curve. In contrast amorphous GST shows a high resistance at low biases while, above a threshold voltage, a transition takes place from a highly resistive to a conductive state, characterized by a negative differential-resistance behavior. A clear and complete understanding of the threshold behavior of the amorphous phase is fundamental for exploiting such materials in the fabrication of innovative nonvolatile memories. The type of feedback that produces the snapback phenomenon is described as a filamentation in energy that is controlled by electron–electron interactions between trapped electrons and band electrons. The model thus derived is implemented within a state-of-the-art simulator. An analytical version of the model is also derived and is useful for discussing the snapback behavior and the scaling properties of the device.

Charge-transport simulations in organic semiconductors

In this thesis we have extended the methods for microscopic charge-transport simulations for organic semiconductors. In these materials the weak intermolecular interactions lead to spatially localized charge carriers, and the charge transport occurs as an activated hopping process between diabatic states. In addition to weak electronic couplings between these states, different electrostatic environments in the organic material lead to a broadening of the density of states for the charge energies which limits carrier mobilities.rnThe contributions to the method development includern(i) the derivation of a bimolecular charge-transfer rate,rn(ii) the efficient evaluation of intermolecular (outer-sphere) reorganization energies,rn(iii) the investigation of effects of conformational disorder on intramolecular reorganization energies or internal site energiesrnand (iv) the inclusion of self-consistent polarization interactions for calculation of charge energies.These methods were applied to study charge transport in amorphous phases of small molecules used in the emission layer of organic light emitting diodes (OLED).rnWhen bulky substituents are attached to an aromatic core in order to adjust energy levels or prevent crystallization, a small amount of delocalization of the frontier orbital to the substituents can increase electronic couplings between neighboring molecules. This leads to improved charge-transfer rates and, hence, larger charge-mobility. We therefore suggest using the mesomeric effect (as opposed to the inductive effect) when attaching substituents to aromatic cores, which is necessary for example in deep blue OLEDs, where the energy levels of a host molecule have to be adjusted to those of the emitter.rnFurthermore, the energy landscape for charges in an amorphous phase cannot be predicted by mesoscopic models because they approximate the realistic morphology by a lattice and represent molecular charge distributions in a multipole expansion. The microscopic approach shows that a polarization-induced stabilization of a molecule in its charged and neutral states can lead to large shifts, broadening, and traps in the distribution of charge energies. These results are especially important for multi-component systems (the emission layer of an OLED or the donor-acceptor interface of an organic solar cell), if the change in polarizability upon charging (or excitation in case of energy transport) is different for the components. Thus, the polarizability change upon charging or excitation should be added to the set of molecular parameters essential for understanding charge and energy transport in organic semiconductors.rnWe also studied charge transport in self-assembled systems, where intermolecular packing motives induced by side chains can increase electronic couplings between molecules. This leads to larger charge mobility, which is essential to improve devices such as organic field effect transistors, where low carrier mobilities limit the switching frequency.rnHowever, it is not sufficient to match the average local molecular order induced by the sidernchains (such as the pitch angle between consecutive molecules in a discotic mesophase) with maxima of the electronic couplings.rnIt is also important to make the corresponding distributions as narrow as possible compared to the window determined by the closest minima of thernelectronic couplings. This is especially important in one-dimensional systems, where charge transport is limited by the smallest electronic couplings.rnThe immediate implication for compound design is that the side chains should assist the self-assemblingrnprocess not only via soft entropic interactions, but also via stronger specific interactions, such as hydrogen bonding.rnrnrnrn

Charge generation and recombination in solid-state dye-sensitized solar cells

Diese Doktorarbeit befasst sich mit Ladungsgeneration und – rekombination in Feststoff-Farbstoffsolarzellen, die spiro-OMeTAD als Lochleiter verwenden. Die vorliegende Arbeit ist in drei Fallstudien unterteilt: i.) Kern-erweiterte Rylen-Farbstoffe, ii.) ein Perylenmonoimid-Farbstoff und iii.) Donor-π verbrückte (Cyclopentadithiophen)-Akzeptor-Farbstoffe. Trotz ihres hohen molaren Extinktionskoeffizienten und der hohen Absorbanz der sensibilisierten Filme, zeigen einige dieser Farbstoffmoleküle nur geringe photovoltaischen Effizienzen. Um den Ursprung des geringen Wirkungsgrades herauszufinden, wurde breitbandige, ultraschnelle transiente Absorptionsspektroskopie an Solarzellen durchgeführt.rnInsbesondere die Auswirkungen verschiedender Ankergruppen, Dipolmomente, Photolumineszenzlebenszeiten, Lithium-Kationensensitivität und Ladungsträgerdynamik, die alle einen großen Einfluss auf den Wirkungsgrad der Solarzelle besitzen, wurden untersucht. In der ersten Fallstudie zeigte ein kurzer Rylen-Farbstoff aufgrund deutlich verlängerter Lebenszeiten die beste Effizienz im Vergleich zu größeren Kern-erweiterten Rylen-Farbstoffen. Die Lebenszeit wurde weiter reduziert, wenn Maleinsäure als Ankergruppe unter einer Ringöffnungsreaktion an die mesoporöse Oberfläche des Metalloxid-Halbleiters adsorbierte. Dies konnte mit Hilfe von Berechnungen mittels der Dichtefunktionaltheorie (DFT, B3LYP) auf die Differenz des Dipolmoments zwischen Grundzustand und angeregtem Zustand zurückgeführt werden. Die Berechnungen bekräftigen die unvorteilhafte Injektion von Ladungen durch die Änderung der Richtung des Dipolmoments, wenn eine Ringöffnung der Anhydridgruppe stattfindet. In der zweiten Studie zeigte das Perylenmonoimid-Derivat ID889 einen Wirkungsgrad von 4.5% in Feststoff-Farbstoffsolarzellen, wobei ID889 sogar ohne Zuhilfenahme eines Additivs in der Lage ist langlebige Farbstoffkationen zu bilden. Die Verwendung von Lithium-Kationen stabilisiert jedoch sowohl den Prozess der Ladungsgeneration als auch den der Ladungsregeneration. Des Weiteren wurde in ID889-sensitivierten Bauteilen kein reduktives Löschen beobachtet. Dabei wurde die Dynamik der Exzitonen mittels einer soft-modelling Methode Kurvenanalyse aus den Daten der transienten Absorptionsspektroskopie gewonnen. Zuletzt wurden Strukturen mit Cyclopentadithiophen(CPDT)-Baustein untersucht, die eine typische D-π-A Molekülstruktur bilden. FPH224 und 233 zeigten dabei eine bessere Effizienz als FPH231 und 303 aufgrund einer großen Injektionseffizienz (IE) und längerer Lebenszeit der angeregten Zustände. Dies kann auf reduktives Löschen in FPH231 und 303 zurückgeführt werden, wohingegen FPH224 und 233 einen moderaten Zerfall des Spirokationensignals zeigten.

Charge induced enhancement of adsorption for hydrogen storage materials

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.

Charge and spin transport in nanoscale junction from first principles

Recently nanoscale junctions consisting of 0-D nanostructures (single molecule) or 1-D nanostructures (semiconducting nanowire) sandwiched between two metal electrodes are successfully fabricated and characterized. What lacks in the recent developments is the understanding of the mechanism behind the observed phenomena at the level of atoms and electrons. For example, the origin of observed switching effect in a semiconducting nanowire due to the influence of an external gate bias is not yet understood at the electronic structure level. On the same context, different experimental groups have reported different signs in tunneling magneto-resistance for the same organic spin valve structure, which has baffled researchers working in this field. In this thesis, we present the answers to some of these subtle questions by investigating the charge and spin transport in different nanoscale junctions. A parameter-free, single particle Green’s function approach in conjunction with a posteriori density functional theory (DFT) involving a hybrid orbital dependent functional is used to calculate the tunneling current in the coherent transport limit. The effect of spin polarization is explicitly incorporated to investigate spin transport in a nanoscale junction. Through the electron transport studies in PbS nanowire junction, a new orbital controlled mechanism behind the switching of the current is proposed. It can explain the switching behavior, not only in PbS nanowire, but in other lead-chalcogenide nanowires as well. Beside this, the electronic structure properties of this nanowire are studied using periodic DFT. The quantum confinement effect was investigated by calculating the bandgap of PbS nanowires with different diameters. Subsequently, we explain an observed semiconducting to metallic phase transition of this nanowire by calculating the bandgap of the nanowire under uniform radial strain. The compressive radial strain on the nanowire was found to be responsible for the metallic to semiconducting phase transition. Apart from studying one dimensional nanostructure, we also present transport properties in zero dimensional single molecular junctions. We proposed a new codoping approach in a single molecular carborane junction, where a cation and an anion are simultaneously doped to find the role of a single atom in the device. The main purpose was to build a molecular junction where a single atom can dictate the flow of electrons in a circuit. Recent observations of both positive and negative sign in tunneling magnetoresistance (TMR) the using same organic spin-valve structure hasmystified researchers. From our spin dependent transport studies in a prototypical organic molecular tunneling device, we found that a 3% change in metal-molecule interfacial distance can alter the sign of TMR. Changing the interfacial distance by 3%, the number of participating eigenstates as well as their orbital characteristic changes for anti-parallel configuration of the magnetization at the two electrodes, leading to the sign reversal of the TMR. Apart from this, the magnetic proximity effect under applied bias is investigated quantitatively, which can be used to understand the observed unexpectedmagnetismin carbon basedmaterials when they are in close proximity with magnetic substrates.

Probing Charge Transfer in Benzodifuran-C-60 Dumbbell-Type Electron Donor-Acceptor Conjugates: Ground- and Excited-State Assays

Rigid electron donor-acceptor conjugates (1-3) that combine -extended benzodifurans as electron donors and C-60 molecules as electron acceptors with different linkers have been synthesized and investigated with respect to intramolecular charge-transfer events. Electrochemistry, fluorescence, and transient absorption measurements revealed tunable and structure-dependent charge-transfer processes in the ground and excited states. Our experimental findings are underpinned by density-functional theory calculations.

Surface charge of polymer coated SPIONs influences the serum protein adsorption, colloidal stability and subsequent cell interaction in vitro

It is known that the nanoparticle-cell interaction strongly depends on the physicochemical properties of the investigated particles. In addition, medium density and viscosity influence the colloidal behaviour of nanoparticles. Here, we show how nanoparticle-protein interactions are related to the particular physicochemical characteristics of the particles, such as their colloidal stability, and how this significantly influences the subsequent nanoparticle-cell interaction in vitro. Therefore, different surface charged superparamagnetic iron oxide nanoparticles were synthesized and characterized. Similar adsorbed protein profiles were identified following incubation in supplemented cell culture media, although cellular uptake varied significantly between the different particles. However, positively charged nanoparticles displayed a significantly lower colloidal stability than neutral and negatively charged particles while showing higher non-sedimentation driven cell-internalization in vitro without any significant cytotoxic effects. The results of this study strongly indicate therefore that an understanding of the aggregation state of NPs in biological fluids is crucial in regards to their biological interaction(s).