Universal Non-Debye Scaling in the Density of States of Amorphous Solids.

At the jamming transition, amorphous packings are known to display anomalous vibrational modes with a density of states (DOS) that remains constant at low frequency. The scaling of the DOS at higher packing fractions remains, however, unclear. One might expect to find a simple Debye scaling, but recent results from effective medium theory and the exact solution of mean-field models both predict an anomalous, non-Debye scaling. Being mean-field in nature, however, these solutions are only strictly valid in the limit of infinite spatial dimension, and it is unclear what value they have for finite-dimensional systems. Here, we study packings of soft spheres in dimensions 3 through 7 and find, away from jamming, a universal non-Debye scaling of the DOS that is consistent with the mean-field predictions. We also consider how the soft mode participation ratio evolves as dimension increases.

Local atomic structure in tetragonal pure ZrO(2) nanopowders

The local atomic structures around the Zr atom of pure (undoped) ZrO(2) nanopowders with different average crystallite sizes, ranging from 7 to 40 nm, have been investigated. The nanopowders were synthesized by different wet-chemical routes, but all exhibit the high-temperature tetragonal phase stabilized at room temperature, as established by synchrotron radiation X-ray diffraction. The extended X-ray absorption fine structure (EXAFS) technique was applied to analyze the local structure around the Zr atoms. Several authors have studied this system using the EXAFS technique without obtaining a good agreement between crystallographic and EXAFS data. In this work, it is shown that the local structure of ZrO(2) nanopowders can be described by a model consisting of two oxygen subshells (4 + 4 atoms) with different Zr-O distances, in agreement with those independently determined by X-ray diffraction. However, the EXAFS study shows that the second oxygen subshell exhibits a Debye-Waller (DW) parameter much higher than that of the first oxygen subshell, a result that cannot be explained by the crystallographic model accepted for the tetragonal phase of zirconia-based materials. However, as proposed by other authors, the difference in the DW parameters between the two oxygen subshells around the Zr atoms can be explained by the existence of oxygen displacements perpendicular to the z direction; these mainly affect the second oxygen subshell because of the directional character of the EXAFS DW parameter, in contradiction to the crystallographic value. It is also established that this model is similar to another model having three oxygen subshells, with a 4 + 2 + 2 distribution of atoms, with only one DW parameter for all oxygen subshells. Both models are in good agreement with the crystal structure determined by X-ray diffraction experiments.

Observation of cooperative Mie scattering from an ultracold atomic cloud

Scattering of light at a distribution of scatterers is an intrinsically cooperative process, which means that the scattering rate and the angular distribution of the scattered light are essentially governed by bulk properties of the distribution, such as its size, shape, and density, although local disorder and density fluctuations may have an important impact on the cooperativity. Via measurements of the radiation pressure force exerted by a far-detuned laser beam on a very small and dense cloud of ultracold atoms, we are able to identify the respective roles of superradiant acceleration of the scattering rate and of Mie scattering in the cooperative process. They lead, respectively, to a suppression or an enhancement of the radiation pressure force. We observe a maximum in the radiation pressure force as a function of the phase shift induced in the incident laser beam by the cloud's refractive index. The maximum marks the borderline of the validity of the Rayleigh-Debye-Gans approximation from a regime, where Mie scattering is more complex. Our observations thus help to clarify the intricate relationship between Rayleigh scattering of light at a coarse-grained ensemble of individual scatterers and Mie scattering at the bulk density distribution.

Epidermal iontophoresis: I. Development of the ionic mobility-pore model

Purpose, An integrated ionic mobility-pore model for epidermal iontophoresis is developed from theoretical considerations using both the free volume and pore restriction forms of the model for a range of solute radii (r(j)) approaching the pore radii (r(p)) as well as approximation of the pore restriction form for r(j)/r(p) < 0.4. In this model, we defined the determinants for iontophoresis as solute size (defined by MV, MW or radius), solute mobility, solute shape, solute charge, the Debye layer thickness, total current applied, solute concentration, fraction ionized, presence of extraneous ions (defined by solvent conductivity), epidermal permselectivity, partitioning rates to account for interaction of unionized and ionized lipophilic solutes with the wall of the pore and electroosmosis. Methods, The ionic mobility-pore model was developed from theoretical considerations to include each of the determinants of iontophoretic transport. The model was then used to reexamine iontophoretic flux conductivity and iontophoretic flux-fraction ionized literature data on the determinants of iontophoretic flux. Results. The ionic mobility-pore model was found to be consistent with existing experimental data and determinants defining iontophoretic transport. However, the predicted effects of solute size on iontophoresis are more consistent with the pore-restriction than free volume form of the model. A reanalysis of iontophoretic flux-conductivity data confirmed the model's prediction that, in the absence of significant electroosmosis, the reciprocal of flux is linearly related to either donor or receptor solution conductivity. Significant interaction with the pore walls, as described by the model, accounted for the reported pH dependence of the iontophoretic transport for a range of ionizable solutes. Conclusions. The ionic mobility-pore iontophoretic model developed enables a range of determinants of iontophoresis to be described in a single unifying equation which recognises a range of determinants of iontophoretic flux.

XAS characterization of the RuO(2)-Ta(2)O(5) system local (crystal) structure

The influence of the preparation method on the structural properties of the RuO(2)-Ta(2)O(5) system was investigated. Both thin films on Ti substrates and powder samples of nominal composition Ti/RuO(2)-Ta(2)O(5) (Ru:Ta = 100:0, 90:10, 80:20, 30:70, and 0:100 at.%) were prepared through thermal decomposition of polymeric precursors (DPP). The thin films and powder samples were investigated using X-ray absorption spectroscopy (XAS). XANES analyses showed that Ru and Ta are present in the Ru(IV) and Ta(V) oxidation states. EXAFS signals of all the samples were analyzed, to obtain the average bond length (r), coordination number, and the Debye-Waller factor (sigma(2)) for each Ru-O, Ru-Ru, Ta-O nearest-neighbor. The first shell Ru-O distance was found at 1.91-1.92 angstrom with coordination number of 1.8-2.1, and at 2.01-2.02 angstrom with coordination number of 3.9-4.1. The Ta-O distance obtained for all the samples and in both modes (transmission and fluorescence) had significantly different values from the theoretical ones. The results revealed that the local structure around both the Ru and Ta sites are similar, and that they consist of distorted M-O(6) octahedra (where M = Ru or Ta). (C) 2010 Elsevier B.V. All rights reserved.

Experimental study of proton induced nuclear reactions in 6,7 Li

This work presents the results of the experimental study of proton induced nuclear reactions in lithium, namely the 7Li(p,α) 4He, 6Li(p,α) 3He and 7Li(p,p)7Li reactions. The amount of 7Li and 6Li identified as primordial and observed in very old stars of the Milky Way galactic halo strongly deviates from the predictions of primordial nucleosynthesis and stellar evolution models which depend, among other factors, on the cross sections of reactions like 7Li(p,α) 4He and 6Li(p,α) 3He. These discrepancies have triggered a large amount of research in the fields of stellar evolution, cosmology, pre-galactic evolution and low energy nuclear reactions. Focusing on nuclear reactions, this work has measured the 7Li(p,α) 4He and 6Li(p,α) 3He reactions cross sections (expressed in terms of the astrophysical S -factor) with higher accuracy, and the electron screening effects in these reactions for different environments (insulators and metallic targets). The 7Li(p,α) 4He angular distributions were also measured. These measurementstook place in two laboratory facilities, in the framework of the LUNA (Laboratory for Undergroud Nuclear Astrophysics) international collaboration, namely the Laboratorio ´ de Feixe de Ioes ˜ in ITN (Instituto Tecnologico ´ e Nuclear) Sacavem, ´ Portugal, and the Dynamitron-TandemLaboratorium in Ruhr-Universitat¨ Bochum, Germany. The ITN target chamber was modified to measure these nuclear reactions, with the design and construction of new components, the addition of one turbomolecular pump and a cold finger. The 7Li(p,α) 4He and 6Li(p,α) 3He reactions were measured concurrently with seven and four targets, respectively. These targets were produced in order to obtain adequate and stable lithium depth profiles. In metallic environments, the measured electron screening potential energies are much higher than the predictions of atomic-physics models. The Debye screening model applied to the metallic conduction electrons is able to explain these high values. It is a simple model, but also very robust. Concerning primordial nucleosynthesis and stellar evolution models, these results are very important as they show that laboratory measurements are well controlled, and the model inputs from these cross sections are therefore correct. In this work the 7Li(p,p)7Li differential cross section was also measured, which is useful to describe the 7Li(p,α) 4He entrance channel.

Influence of constraining and confinement in the molecular mobility of low molecular weight materials

Dissertation presented to obtain a Ph.D. Degree in Chemical Physics

Analytical and numerical study of the electro-osmotic annular flow of viscoelastic fluids

In this work we present semi-analytical solutions for the electro-osmotic annular flow of viscoelastic fluids modeled by the Linear and Exponential PTT models. The viscoelastic fluid flows in the axial direction between two concentric cylinders under the combined influences of electrokinetic and pressure forcings. The analysis invokes the Debye-Hückel approximation and includes the limit case of pure electro-osmotic flow. The solution is valid for both no slip and slip velocity at the walls and the chosen slip boundary condition is the linear Navier slip velocity model. The combined effects of fluid rheology, electro-osmotic and pressure gradient forcings on the fluid velocity distribution are also discussed.

Vacancy and interstitial depth profiles in ion-implanted silicon

An experimental method of studying shifts between concentration-versus-depth profiles of vacancy- and interstitial-type defects in ion-implanted silicon is demonstrated. The concept is based on deep level transient spectroscopy measurements utilizing the filling pulse variation technique. The vacancy profile, represented by the vacancy¿oxygen center, and the interstitial profile, represented by the interstitial carbon¿substitutional carbon pair, are obtained at the same sample temperature by varying the duration of the filling pulse. The effect of the capture in the Debye tail has been extensively studied and taken into account. Thus, the two profiles can be recorded with a high relative depth resolution. Using low doses, point defects have been introduced in lightly doped float zone n-type silicon by implantation with 6.8 MeV boron ions and 680 keV and 1.3 MeV protons at room temperature. The effect of the angle of ion incidence has also been investigated. For all implantation conditions the peak of the interstitial profile is displaced towards larger depths compared to that of the vacancy profile. The amplitude of this displacement increases as the width of the initial point defect distribution increases. This behavior is explained by a simple model where the preferential forward momentum of recoiling silicon atoms and the highly efficient direct recombination of primary point defects are taken into account.

Majority carrier capture cross section determination in the large deep trap concentration cases

A method to determine the thermal cross section of a deep level from capacitance measurements is reported. The results enable us to explain the nonexponential behavior of the capacitance versus capture time when the trap concentration is not negligible with respect to that of the shallow one, and the Debye tail effects are taken into account. A figure of merit for the nonexponential behavior of the capture process is shown and discussed for different situations of doping and applied bias. We have also considered the influence of the position of the trap level"s energy on the nonexponentiality of the capture transient. The experimental results are given for the gold acceptor level in silicon and for the DX center in Al0.55 Ga0.45As, which are in good agreement with the developed theory.

A Thermokinetic approach to radiative heat transfer at the nanoscale

Radiative heat exchange at the nanoscale presents a challenge for several areas due to its scope and nature. Here, we provide a thermokinetic description of microscale radiative energy transfer including phonon-photon coupling manifested through a non-Debye relaxation behavior. We show that a lognormal-like distribution of modes of relaxation accounts for this non-Debye relaxation behavior leading to the thermal conductance. We also discuss the validity of the fluctuation-dissipation theorem. The general expression for the thermal conductance we obtain fits existing experimental results with remarkable accuracy. Accordingly, our approach offers an overall explanation of radiative energy transfer through micrometric gaps regardless of geometrical configurations and distances.

Elastic properties and secondary structure formation of single-stranded DNA at monovalent and divalent salt conditions

Single-stranded DNA (ssDNA) plays a major role in several biological processes. It is therefore of fundamental interest to understand how the elastic response and the formation of secondary structures are modulated by the interplay between base pairing and electrostatic interactions. Here we measure force-extension curves (FECs) of ssDNA molecules in optical tweezers set up over two orders of magnitude of monovalent and divalent salt conditions, and obtain its elastic parameters by fitting the FECs to semiflexible models of polymers. For both monovalent and divalent salts, we find that the electrostatic contribution to the persistence length is proportional to the Debye screening length, varying as the inverse of the square root of cation concentration. The intrinsic persistence length is equal to 0.7 nm for both types of salts, and the effectivity of divalent cations in screening electrostatic interactions appears to be 100-fold as compared with monovalent salt, in line with what has been recently reported for single-stranded RNA. Finally, we propose an analysis of the FECs using a model that accounts for the effective thickness of the filament at low salt condition and a simple phenomenological description that quantifies the formation of non-specific secondary structure at low forces.

Potentiometric titration as a method of determining the stoichiometric dissociation constants of weak acids from the thermodynamic dissociation constants of aqueous solutions at 298.15 K

The simple single-ion activity coefficient equation originating from the Debye-Hückel theory was used to determine the thermodynamic and stoichiometric dissociation constants of weak acids from data concerning galvanic cells. Electromotive force data from galvanic cells without liquid junctions, which was obtained from literature, was studied in conjuction with the potentiometric titration data relating to aqueous solutions at 298.15 K. The dissociation constants of weak acids could be determined by the presented techniques and almost all the experimental data studied could be interpreted within the range of experimental error. Potentiometric titration has been used here and the calculation methods were developed to obtain the thermodynamic and stoichiometric dissociation constants of some weak acids in aqueous solutions at 298.15 K. The ionic strength of titrated solutions were adjusted using an inert electrolyte, namely, sodium or potassium chloride. Salt content alonedetermines the ionic strength. The ionic strength of the solutions studied varied from 0.059 mol kg-1 to 0.37 mol kg-1, and in some cases up to 1.0 mol kg-1. The following substances were investigated using potentiometric titration: aceticacid, propionic acid, L-aspartic acid, L-glutamic acid and bis(2,2-dimethyl-3-oxopropanol) amine.

Elastic properties and secondary structure formation of single-stranded DNA at monovalent and divalent salt conditions

Single-stranded DNA (ssDNA) plays a major role in several biological processes. It is therefore of fundamental interest to understand how the elastic response and the formation of secondary structures are modulated by the interplay between base pairing and electrostatic interactions. Here we measure force-extension curves (FECs) of ssDNA molecules in optical tweezers set up over two orders of magnitude of monovalent and divalent salt conditions, and obtain its elastic parameters by fitting the FECs to semiflexible models of polymers. For both monovalent and divalent salts, we find that the electrostatic contribution to the persistence length is proportional to the Debye screening length, varying as the inverse of the square root of cation concentration. The intrinsic persistence length is equal to 0.7 nm for both types of salts, and the effectivity of divalent cations in screening electrostatic interactions appears to be 100-fold as compared with monovalent salt, in line with what has been recently reported for single-stranded RNA. Finally, we propose an analysis of the FECs using a model that accounts for the effective thickness of the filament at low salt condition and a simple phenomenological description that quantifies the formation of non-specific secondary structure at low forces.

Effect of long-range Coulomb interaction on shot-noise suppression in ballistic transport

We present a microscopic analysis of shot-noise suppression due to long-range Coulomb interaction in semiconductor devices under ballistic transport conditions. An ensemble Monte Carlo simulator self-consistently coupled with a Poisson solver is used for the calculations. A wide range of injection-rate densities leading to different degrees of suppression is investigated. A sharp tendency of noise suppression at increasing injection densities is found to scale with a dimensionless Debye length related to the importance of space-charge effects in the structure.