Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid–fluid molecular parameters for the system amorphous silica–Ar and amorphous silica–N2, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.

Adsorption of N-2, Ar, acetone, chloroform and acetone-chloroform mixture on carbon black in the framework of molecular layer structure theory (MLST)

Adsorption of pure nitrogen, argon, acetone, chloroform and acetone-chloroform mixture on graphitized thermal carbon black is considered at sub-critical conditions by means of molecular layer structure theory (MLST). In the present version of the MLST an adsorbed fluid is considered as a sequence of 2D molecular layers, whose Helmholtz free energies are obtained directly from the analysis of experimental adsorption isotherm of pure components. The interaction of the nearest layers is accounted for in the framework of mean field approximation. This approach allows quantitative correlating of experimental nitrogen and argon adsorption isotherm both in the monolayer region and in the range of multi-layer coverage up to 10 molecular layers. In the case of acetone and chloroform the approach also leads to excellent quantitative correlation of adsorption isotherms, while molecular approaches such as the non-local density functional theory (NLDFT) fail to describe those isotherms. We extend our new method to calculate the Helmholtz free energy of an adsorbed mixture using a simple mixing rule, and this allows us to predict mixture adsorption isotherms from pure component adsorption isotherms. The approach, which accounts for the difference in composition in different molecular layers, is tested against the experimental data of acetone-chloroform mixture (non-ideal mixture) adsorption on graphitized thermal carbon black at 50 degrees C. (C) 2005 Elsevier Ltd. All rights reserved.

Pore size characterization of mesoporous materials by a thermodynamic approach: A curvature-dependent solid-fluid potential

A thermodynamic analysis of nitrogen adsorption in cylindrical pores of MCM-41 and SBA-15 samples at 77 K is presented within the framework of the Broekhoff and de Boer (BdB) theory. We accounted for the effect of the solid surface curvature on the potential exerted by the pore walls. The developed model is in quantitative agreement with the non-local density functional theory (NLDFT) for pores larger than 2 tun. This modified BdB theory accounting for the Curvature Dependent Potential (CDP-BdB) was applied to determine the pore size distribution (PSD) of a number of MCM-41 and SBA-15 samples on the basis of matching the equilibrium theoretical isotherm against the adsorption branch of the experimental isotherm. In all cases investigated the PSDs determined with the new approach are very similar to those determined with the non-local density functional theory also using the same basis of matching of theoretical isotherm against the experimental adsorption branch. The developed continuum theory is very simple in its utilization, suggesting that CDP-BdB could be used as an alternative tool to obtain PSD for mesoporous solids from the analysis of adsorption branch of adsorption isotherms of any sub-critical fluids.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

Towards sea surface pollution detection from visible band images

This paper presents a novel approach to water pollution detection from remotely sensed low-platform mounted visible band camera images. We examine the feasibility of unsupervised segmentation for slick (oily spills on the water surface) region labelling. Adaptive and non adaptive filtering is combined with density modeling of the obtained textural features. A particular effort is concentrated on the textural feature extraction from raw intensity images using filter banks and adaptive feature extraction from the obtained output coefficients. Segmentation in the extracted feature space is achieved using Gaussian mixture models (GMM).

Ontology-based protein-protein interactions extraction from literature using the hidden vector state model

This paper proposes a novel framework of incorporating protein-protein interactions (PPI) ontology knowledge into PPI extraction from biomedical literature in order to address the emerging challenges of deep natural language understanding. It is built upon the existing work on relation extraction using the Hidden Vector State (HVS) model. The HVS model belongs to the category of statistical learning methods. It can be trained directly from un-annotated data in a constrained way whilst at the same time being able to capture the underlying named entity relationships. However, it is difficult to incorporate background knowledge or non-local information into the HVS model. This paper proposes to represent the HVS model as a conditionally trained undirected graphical model in which non-local features derived from PPI ontology through inference would be easily incorporated. The seamless fusion of ontology inference with statistical learning produces a new paradigm to information extraction.

High performance numerical modeling of ultra-short laser pulse propagation based on multithreaded parallel hardware

The focus of this study is development of parallelised version of severely sequential and iterative numerical algorithms based on multi-threaded parallel platform such as a graphics processing unit. This requires design and development of a platform-specific numerical solution that can benefit from the parallel capabilities of the chosen platform. Graphics processing unit was chosen as a parallel platform for design and development of a numerical solution for a specific physical model in non-linear optics. This problem appears in describing ultra-short pulse propagation in bulk transparent media that has recently been subject to several theoretical and numerical studies. The mathematical model describing this phenomenon is a challenging and complex problem and its numerical modeling limited on current modern workstations. Numerical modeling of this problem requires a parallelisation of an essentially serial algorithms and elimination of numerical bottlenecks. The main challenge to overcome is parallelisation of the globally non-local mathematical model. This thesis presents a numerical solution for elimination of numerical bottleneck associated with the non-local nature of the mathematical model. The accuracy and performance of the parallel code is identified by back-to-back testing with a similar serial version.

Are indigenous approaches to achieving influence in business organizations distinctive? A comparative study of guanxi, wasta, jeitinho, svyazi and pulling strings

Managers in five nations rated scenarios exemplifying indigenous forms of informal influence whose cultural origins were concealed. Locally generated scenarios illustrated episodes of guanxi, wasta, jeitinho, svyazi and pulling strings. Local scenarios were judged representative of local influence processes but so too were some scenarios derived from other contexts. Furthermore, many scenarios were rated as more typical in non-local contexts. While these influence processes are found to be widely disseminated, they occur more frequently in contexts characterized by high self-enhancement values, low self-transcendence values and high endorsement of business corruptibility. Implications for a fuller understanding of local business practices are discussed. © 2012 Copyright Taylor and Francis Group, LLC.

Evolution of timing jitter in nonlinearly-guided, dispersion managed transmission systems

Timing jitter is a major factor limiting the performance of any high-speed, long-haul data transmission system. It arises from a number of reasons, such as interaction with accumulated spontaneous emission, inter-symbol interference (ISI), electrostriction etc. Some effects causing timing jitter can be reduced by means of non-linear filtering, using, for example, a nonlinear optical loop mirror (NOLM) [1]. The NOLM has been shown to reduce the timing jitter by suppressing the ASE and by stabilising the pulse duration [2, 3]. In this paper, we investigate the dynamics of timing jitter in a 2R regenerated system, nonlinearly guided by NOLMs at bit rates of 10, 20, 40, and 80- Gbit/s. Transmission performance of an equivalent non-regenerated (generic) system is taken as a reference.

Inhomogeneous Fractional Diffusion Equations

2000 Mathematics Subject Classification: Primary 26A33; Secondary 35S10, 86A05

Exact Solutions of Nonlocal Boundary Value Problems for One- and Two-Dimensional Heat Equation

Иван Хр. Димовски, Юлиан Ц. Цанков - Предложен е метод за намиране на явни решения на клас двумерни уравнения на топлопроводността с нелокални условия по пространствените променливи. Методът е основан на директно тримерно операционно смятане. Класическата дюамелова конволюция е комбинирана с две некласически конволюции за операторите ∂xx и ∂yy в една тримерна конволюция. Съответното операционно смятане използва мултипликаторни частни. Мултипликаторните частни позволяват да се продължи принципът на Дюамел за пространствените променливи и да се намерят явни решения на разглежданите гранични задачи. Общите разглеждания са приложени в случая на гранични условия от типа на Йонкин. Намерени са експлицитни решения в затворен вид.

Application of Numerical Methods to Study Arrangement and Fracture of Lithium-Ion Microstructure

The focus of this work is to develop and employ numerical methods that provide characterization of granular microstructures, dynamic fragmentation of brittle materials, and dynamic fracture of three-dimensional bodies.

We first propose the fabric tensor formalism to describe the structure and evolution of lithium-ion electrode microstructure during the calendaring process. Fabric tensors are directional measures of particulate assemblies based on inter-particle connectivity, relating to the structural and transport properties of the electrode. Applying this technique to X-ray computed tomography of cathode microstructure, we show that fabric tensors capture the evolution of the inter-particle contact distribution and are therefore good measures for the internal state of and electronic transport within the electrode.

We then shift focus to the development and analysis of fracture models within finite element simulations. A difficult problem to characterize in the realm of fracture modeling is that of fragmentation, wherein brittle materials subjected to a uniform tensile loading break apart into a large number of smaller pieces. We explore the effect of numerical precision in the results of dynamic fragmentation simulations using the cohesive element approach on a one-dimensional domain. By introducing random and non-random field variations, we discern that round-off error plays a significant role in establishing a mesh-convergent solution for uniform fragmentation problems. Further, by using differing magnitudes of randomized material properties and mesh discretizations, we find that employing randomness can improve convergence behavior and provide a computational savings.

The Thick Level-Set model is implemented to describe brittle media undergoing dynamic fragmentation as an alternative to the cohesive element approach. This non-local damage model features a level-set function that defines the extent and severity of degradation and uses a length scale to limit the damage gradient. In terms of energy dissipated by fracture and mean fragment size, we find that the proposed model reproduces the rate-dependent observations of analytical approaches, cohesive element simulations, and experimental studies.

Lastly, the Thick Level-Set model is implemented in three dimensions to describe the dynamic failure of brittle media, such as the active material particles in the battery cathode during manufacturing. The proposed model matches expected behavior from physical experiments, analytical approaches, and numerical models, and mesh convergence is established. We find that the use of an asymmetrical damage model to represent tensile damage is important to producing the expected results for brittle fracture problems.

The impact of this work is that designers of lithium-ion battery components can employ the numerical methods presented herein to analyze the evolving electrode microstructure during manufacturing, operational, and extraordinary loadings. This allows for enhanced designs and manufacturing methods that advance the state of battery technology. Further, these numerical tools have applicability in a broad range of fields, from geotechnical analysis to ice-sheet modeling to armor design to hydraulic fracturing.

The VLT-FLAMES Tarantula Survey: XIX. B-type supergiants: Atmospheric parameters and nitrogen abundances to investigate the role of binarity and the width of the main sequence

Context: Model atmosphere analyses have been previously undertaken for both Galactic and extragalactic B-type supergiants. By contrast, little attention has been given to a comparison of the properties of single supergiants and those that are members of multiple systems. 

Aims: Atmospheric parameters and nitrogen abundances have been estimated for all the B-type supergiants identified in the VLT-FLAMES Tarantula survey. These include both single targets and binary candidates. The results have been analysed to investigate the role of binarity in the evolutionary history of supergiants. 

Methods: tlusty non-local thermodynamic equilibrium (LTE) model atmosphere calculations have been used to determine atmospheric parameters and nitrogen abundances for 34 single and 18 binary supergiants. Effective temperatures were deduced using the silicon balance technique, complemented by the helium ionisation in the hotter spectra. Surface gravities were estimated using Balmer line profiles and microturbulent velocities deduced using the silicon spectrum. Nitrogen abundances or upper limits were estimated from the Nii spectrum. The effects of a flux contribution from an unseen secondary were considered for the binary sample. Results. We present the first systematic study of the incidence of binarity for a sample of B-type supergiants across the theoretical terminal age main sequence (TAMS). To account for the distribution of effective temperatures of the B-type supergiants it may be necessary to extend the TAMS to lower temperatures. This is also consistent with the derived distribution of mass discrepancies, projected rotational velocities and nitrogen abundances, provided that stars cooler than this temperature are post-red supergiant objects. For all the supergiants in the Tarantula and in a previous FLAMES survey, the majority have small projected rotational velocities. The distribution peaks at about 50 km s^-1 with 65% in the range 30 km s^-1 ≤ ν_e sin i ≤ 60 km s^-1. About ten per cent have larger ve sin i (≥100 km s^-1), but surprisingly these show little or no nitrogen enhancement. All the cooler supergiants have low projected rotational velocities of ≤70 km s^-1 and high nitrogen abundance estimates, implying that either bi-stability braking or evolution on a blue loop may be important. Additionally, there is a lack of cooler binaries, possibly reflecting the small sample sizes. Single-star evolutionary models, which include rotation, can account for all of the nitrogen enhancement in both the single and binary samples. The detailed distribution of nitrogen abundances in the single and binary samples may be different, possibly reflecting differences in their evolutionary history. 

Conclusions: The first comparative study of single and binary B-type supergiants has revealed that the main sequence may be significantly wider than previously assumed, extending to T_eff = 20 000 K. Some marginal differences in single and binary atmospheric parameters and abundances have been identified, possibly implying non-standard evolution for some of the sample. This sample as a whole has implications for several aspects of our understanding of the evolutionary status of blue supergiants.

Bumps, breathers, and waves in a neural network with spike frequency adaptation

In this Letter we introduce a continuum model of neural tissue that include the effects of so-called spike frequency adaptation (SFA). The basic model is an integral equation for synaptic activity that depends upon the non-local network connectivity, synaptic response, and firing rate of a single neuron. A phenomenological model of SFA is examined whereby the firing rate is taken to be a simple state-dependent threshold function. As in the case without SFA classical Mexican-Hat connectivity is shown to allow for the existence of spatially localized states (bumps). Importantly an analysis of bump stability using recent Evans function techniques shows that bumps may undergo instabilities leading to the emergence of both breathers and traveling waves. Moreover, a similar analysis for traveling pulses leads to the conditions necessary to observe a stable traveling breather. Direct numerical simulations both confirm our theoretical predictions and illustrate the rich dynamic behavior of this model, including the appearance of self-replicating bumps.