Long-range Coulomb interactions and nanoscale electronic inhomogeneities in correlated oxides

Electronic, magnetic, or structural inhomogeneities ranging in size from nanoscopic to mesoscopic scales seem endemic and are possibly generic to colossal magnetoresistance manganites and other transition metal oxides. They are hence of great current interest and understanding them is of fundamental importance. We show here that an extension, to include long-range Coulomb interactions, of a quantum two-fluid l-b model proposed recently for manganites [Phys. Rev. Lett. 92, 157203 (2004)] leads to an excellent description of such inhomogeneities. In the l-b model two very different kinds of electronic states, one localized and polaronic (l) and the other extended or broad band (b) coexist. For model parameters appropriate to manganites and even within a simple dynamical mean-field theory (DMFT) framework, it describes many of the unusual phenomena seen in manganites, including colossal magnetoresistance (CMR), qualitatively and quantitatively. However, in the absence of long-ranged Coulomb interaction, a system described by such a model would actually phase separate, into macroscopic regions of l and b electrons, respectively. As we show in this paper, in the presence of Coulomb interactions, the macroscopic phase separation gets suppressed and instead nanometer scale regions of polarons interspersed with band electron puddles appear, constituting a kind of quantum Coulomb glass. We characterize the size scales and distribution of the inhomogeneity using computer simulations. For realistic values of the long-range Coulomb interaction parameter V-0, our results for the thresholds for occupancy of the b states are in agreement with, and hence support, the earlier approach mentioned above based on a configuration averaged DMFT treatment which neglects V-0; but the present work has features that cannot be addressed in the DMFT framework. Our work points to an interplay of strong correlations, long-range Coulomb interaction, and dopant ion disorder, all inevitably present in transition metal oxides as the origin of nanoscale inhomogeneities rather than disorder frustrated phase competition as is generally believed. As regards manganites, it argues against explanations for CMR based on disorder frustrated phase separation and for an intrinsic origin of CMR. Based on this, we argue that the observed micrometer (meso) scale inhomogeneities owe their existence to extrinsic causes, e.g., strain due to cracks and defects. We suggest possible experiments to validate our speculation.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

Thermodynamics of Al(1-x)Ga(x)N solid solution: Inclination for phase separation and ordering

Although Al(1-x)Ga(x)N semiconductors are used in lighting, displays and high-power amplifiers, there is no experimental thermodynamic information on nitride solid solutions. Thermodynamic data are useful for assessing the intrinsic stability of the solid solution with respect to phase separation and extrinsic stability in relation to other phases such as metallic contacts. The activity of GaN in Al(1-x)Ga(x)N solid solution is determined at 1100 K using a solid-state electrochemical cell: Ga + Al(1-x)Ga(x)N/Fe, Ca(3)N(2)//CaF(2)//Ca(3)N(2), N(2) (0.1 MPa), Fe. The solid-state cell is based on single crystal CaF(2) as the electrolyte and Ca(3)N(2) as the auxiliary electrode to convert the nitrogen chemical potential established by the equilibrium between Ga and Al(1-x)Ga(x)N solid solution into an equivalent fluorine potential. Excess Gibbs free energy of mixing of the solid solution is computed from the results. Results suggest an unusual mixing behavior: a mild tendency for ordering at three discrete compositions (x = 0.25, 0.5 and 0.75) superimposed on predominantly positive deviation from ideality. The lattice parameters exhibit slight deviation from Vegard's law, with the a-parameter showing positive and the c-parameter negative deviation. Although the solid solution is stable in the full range of compositions at growth temperatures, thermodynamic instability is indicated at temperatures below 410 K in the composition range 0.26 <= x <= 0.5. At 355 K, two biphasic regions appear, with terminal solid solutions stable only for 0 <= x <= 0.26 and 0.66 <= x <= 1. The range of terminal solid solubility reduces with decreasing temperature. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of dimerization on dynamics of spin-charge separation in Pariser-Parr-Pople model: A time-dependent density matrix renormalization group study

We investigate the effect of static electron-phonon coupling on real-time dynamics of spin and charge transport in pi-conjugated polyene chains. The polyene chain is modeled by the Pariser-Parr-Pople Hamiltonian with dimerized nearest-neighbor parameter t(0)(1 + delta) for short bonds and t(0)(1 - delta) for long bonds, and long-range electron-electron interactions. We follow the time evolution of the spin and charge using time-dependent density matrix renormalization group technique when a hole is injected at one end of the chain in its ground state. We find that spin and charge dynamics followed through spin and charge velocities depend both on chain length and extent of dimerization delta. Analysis of the results requires focusing on physical quantities such as average spin and charge polarizations, particularly in the large dimerization limit. In the dimerization range 0.0 <= delta <= 0.15, spin-charge dynamics is found to have a well-defined behavior, with spin-charge separation (measured as the ratio of charge velocity to spin velocity) as well as the total amount of charge and spin transported in a given time along the chain decreasing as dimerization increases. However, in the range 0.3 <= delta <= 0.5, it is observed that the dynamics of spin and charge transport becomes complicated. It is observed that, for large delta values, spin-charge separation is suppressed and the injected hole fails to travel the entire length of the chain.

Orientational order as the origin of the long-range hydrophobic effect

The long range attractive force between two hydrophobic surfaces immersed in water is observed to decrease exponentially with their separation-this distance-dependence of effective force is known as the hydrophobic force law (HFL). We explore the microscopic origin of HFL by studying distance-dependent attraction between two parallel rods immersed in 2D Mercedes Benz model of water. This model is found to exhibit a well-defined HFL. Although the phenomenon is conventionally explained by density-dependent theories, we identify orientation, rather than density, as the relevant order parameter. The range of density variation is noticeably shorter than that of orientational heterogeneity. The latter is comparable to the observed distances of hydrophobic force. At large separation, attraction between the rods arises primarily from a destructive interference among the inwardly propagating oppositely oriented heterogeneity generated in water by the two rods. As the rods are brought closer, the interference increases leading to a decrease in heterogeneity and concomitant decrease in free energy of the system, giving rise to the effective attraction. We notice formation of hexagonal ice-like structures at the onset of attractive region which suggests that metastable free energy minimum may play a role in the origin of HFL. (C) 2015 AIP Publishing LLC.

Toughness Of Ni/Al2O3 Interfaces As Dependent On Micron-Scale Plasticity And Atomistic-Scale Separation

Ceramic/metal interfaces were studied that fail by atomistic separation accompanied by plastic dissipation in the metal. The macroscopic toughness of the specific Ni alloy/Al2O3 interface considered is typically on the order of ten times the atomistic work of separation in mode I and even higher if combinations of mode I and mode II act on the interface. Inputs to the computational model of interface toughness are: (i) strain gradient plasticity applied to the Ni alloy with a length parameter determined by an indentation test, and (ii) a potential characterizing mixed mode separation of the interface fit to atomistic results. The roles of the several length parameters in the strain gradient plasticity are determined for indentation and crack growth. One of the parameters is shown to be of dominant importance, thus establishing that indentation can be used to measure the relevant length parameter. Recent results for separation of Ni/Al2O3 interfaces computed by atomistic methods are reviewed, including a set of results computed for mixed mode separation. An approximate potential fit to these results is characterized by the work of separation, the peak separation stress for normal separation and the traction-displacement relation in pure shearing of the interface. With these inputs, the model for steady-state crack growth is used to compute the toughness of the interface under mode I and under the full range of mode mix. The effect of interface strength and the work of separation on macroscopic toughness is computed. Fundamental implications for plasticity-enhanced toughness emerge.

Effects of physical parameter range on dimensionless variable sensitivity in water flooding reservoirs

The similarity criterion for water flooding reservoir flows is concerned with in the present paper. When finding out all the dimensionless variables governing this kind of flow, their physical meanings are subsequently elucidated. Then, a numerical approach of sensitivity analysis is adopted to quantify their corresponding dominance degree among the similarity parameters. In this way, we may finally identify major scaling law in different parameter range and demonstrate the respective effects of viscosity, permeability and injection rate.

Effects of physical parameter range on dimensionless variable sensitivity in water flooding reservoirs

The similarity criterion for water flooding reservoir flows is concerned with in the present paper. When finding out all the dimensionless variables governing this kind of flow, their physical meanings are subsequently elucidated. Then, a numerical approach of sensitivity analysis is adopted to quantify their corresponding dominance degree among the similarity parameters. In this way, we may finally identify major scaling law in different parameter range and demonstrate the respective effects of viscosity, permeability and injection rate.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.

Optimization and parameter study for chiral separation by capillary electrophoresis

Orthogonal design and uniform design were used for the optimization of separation of enantiomers using 2,6-di-O-methyl-beta-cyclodextrin (DM-beta-CD) as a chiral selector by capillary zone electrophoresis, The concentration of DM-beta-CD, buffer pH, running voltage, and capillary temperature were selected as variable parameters, their different effects on peak resolution were studied by the design methods. It was concluded that orthogonal design offers a rapid and efficient means for testing the importance of individual parameters and for determining the optimum operating conditions. However, for a large number of both factors and levels, uniform design is more efficient, The effect of addition of methanol and citric acid buffer on the separation of enantiomers was also examined.

Measurement of the elastic electron-proton cross section and separation of the electric and magnetic form factor in the Q 2 range from 0.004 to 1 (GeV/c) 2

The electromagnetic form factors of the proton are fundamental quantities sensitive to the distribution of charge and magnetization inside the proton. Precise knowledge of the form factors, in particular of the charge and magnetization radii provide strong tests for theory in the non-perturbative regime of QCD. However, the existing data at Q^2 below 1 (GeV/c)^2 are not precise enough for a hard test of theoretical predictions.rnrnFor a more precise determination of the form factors, within this work more than 1400 cross sections of the reaction H(e,e′)p were measured at the Mainz Microtron MAMI using the 3-spectrometer-facility of the A1-collaboration. The data were taken in three periods in the years 2006 and 2007 using beam energies of 180, 315, 450, 585, 720 and 855 MeV. They cover the Q^2 region from 0.004 to 1 (GeV/c)^2 with counting rate uncertainties below 0.2% for most of the data points. The relative luminosity of the measurements was determined using one of the spectrometers as a luminosity monitor. The overlapping acceptances of the measurements maximize the internal redundancy of the data and allow, together with several additions to the standard experimental setup, for tight control of systematic uncertainties.rnTo account for the radiative processes, an event generator was developed and implemented in the simulation package of the analysis software which works without peaking approximation by explicitly calculating the Bethe-Heitler and Born Feynman diagrams for each event.rnTo separate the form factors and to determine the radii, the data were analyzed by fitting a wide selection of form factor models directly to the measured cross sections. These fits also determined the absolute normalization of the different data subsets. The validity of this method was tested with extensive simulations. The results were compared to an extraction via the standard Rosenbluth technique.rnrnThe dip structure in G_E that was seen in the analysis of the previous world data shows up in a modified form. When compared to the standard-dipole form factor as a smooth curve, the extracted G_E exhibits a strong change of the slope around 0.1 (GeV/c)^2, and in the magnetic form factor a dip around 0.2 (GeV/c)^2 is found. This may be taken as indications for a pion cloud. For higher Q^2, the fits yield larger values for G_M than previous measurements, in agreement with form factor ratios from recent precise polarized measurements in the Q2 region up to 0.6 (GeV/c)^2.rnrnThe charge and magnetic rms radii are determined as rn⟨r_e⟩=0.879 ± 0.005(stat.) ± 0.004(syst.) ± 0.002(model) ± 0.004(group) fm,rn⟨r_m⟩=0.777 ± 0.013(stat.) ± 0.009(syst.) ± 0.005(model) ± 0.002(group) fm.rnThis charge radius is significantly larger than theoretical predictions and than the radius of the standard dipole. However, it is in agreement with earlier results measured at the Mainz linear accelerator and with determinations from Hydrogen Lamb shift measurements. The extracted magnetic radius is smaller than previous determinations and than the standard-dipole value.

Controlled rate thermal analysis of sepiolite

CRTA technology offers better resolution and a more detailed interpretation of the decomposition processes of a clay mineral such as sepiolite via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of non-isothermal nature reveal changes in the sepiolite as the sepiolite is converted to an anhydride. In the dynamic experiment two dehydration steps are observed over the ~20-170 and 170-350°C temperature range. In the dynamic experiment three dehydroxylation steps are observed over the temperature ranges 201-337, 337-638 and 638-982°C. The CRTA technology enables the separation of the thermal decomposition steps.

Controlled Rate Thermal analysis of sepiolite

Controlled rate thermal analysis (CRTA) technology offers better resolution and a more detailed interpretation of the decomposition processes of a clay mineral such as sepiolite via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of non-isothermal nature reveal changes in the sepiolite as the sepiolite is converted to an anhydride. In the dynamic experiment two dehydration steps are observed over the *20–170 and 170–350 �C temperature range. In the dynamic experiment three dehydroxylation steps are observed over the temperature ranges 201–337, 337–638 and 638–982 �C. The CRTA technology enables the separation of the thermal decomposition steps.

Determining a set of surrogate parameters to evaluate urban stormwater quality

This thesis details methodology to estimate urban stormwater quality based on a set of easy to measure physico-chemical parameters. These parameters can be used as surrogate parameters to estimate other key water quality parameters. The key pollutants considered in this study are nitrogen compounds, phosphorus compounds and solids. The use of surrogate parameter relationships to evaluate urban stormwater quality will reduce the cost of monitoring and so that scientists will have added capability to generate a large amount of data for more rigorous analysis of key urban stormwater quality processes, namely, pollutant build-up and wash-off. This in turn will assist in the development of more stringent stormwater quality mitigation strategies. The research methodology was based on a series of field investigations, laboratory testing and data analysis. Field investigations were conducted to collect pollutant build-up and wash-off samples from residential roads and roof surfaces. Past research has identified that these impervious surfaces are the primary pollutant sources to urban stormwater runoff. A specially designed vacuum system and rainfall simulator were used in the collection of pollutant build-up and wash-off samples. The collected samples were tested for a range of physico-chemical parameters. Data analysis was conducted using both univariate and multivariate data analysis techniques. Analysis of build-up samples showed that pollutant loads accumulated on road surfaces are higher compared to the pollutant loads on roof surfaces. Furthermore, it was found that the fraction of solids smaller than 150 ìm is the most polluted particle size fraction in solids build-up on both roads and roof surfaces. The analysis of wash-off data confirmed that the simulated wash-off process adopted for this research agrees well with the general understanding of the wash-off process on urban impervious surfaces. The observed pollutant concentrations in wash-off from road surfaces were different to pollutant concentrations in wash-off from roof surfaces. Therefore, firstly, the identification of surrogate parameters was undertaken separately for roads and roof surfaces. Secondly, a common set of surrogate parameter relationships were identified for both surfaces together to evaluate urban stormwater quality. Surrogate parameters were identified for nitrogen, phosphorus and solids separately. Electrical conductivity (EC), total organic carbon (TOC), dissolved organic carbon (DOC), total suspended solids (TSS), total dissolved solids (TDS), total solids (TS) and turbidity (TTU) were selected as the relatively easy to measure parameters. Consequently, surrogate parameters for nitrogen and phosphorus were identified from the set of easy to measure parameters for both road surfaces and roof surfaces. Additionally, surrogate parameters for TSS, TDS and TS which are key indicators of solids were obtained from EC and TTU which can be direct field measurements. The regression relationships which were developed for surrogate parameters and key parameter of interest were of a similar format for road and roof surfaces, namely it was in the form of simple linear regression equations. The identified relationships for road surfaces were DTN-TDS:DOC, TP-TS:TOC, TSS-TTU, TDS-EC and TSTTU: EC. The identified relationships for roof surfaces were DTN-TDS and TSTTU: EC. Some of the relationships developed had a higher confidence interval whilst others had a relatively low confidence interval. The relationships obtained for DTN-TDS, DTN-DOC, TP-TS and TS-EC for road surfaces demonstrated good near site portability potential. Currently, best management practices are focussed on providing treatment measures for stormwater runoff at catchment outlets where separation of road and roof runoff is not found. In this context, it is important to find a common set of surrogate parameter relationships for road surfaces and roof surfaces to evaluate urban stormwater quality. Consequently DTN-TDS, TS-EC and TS-TTU relationships were identified as the common relationships which are capable of providing measurements of DTN and TS irrespective of the surface type.