Application of density functional theory to analysis of energetic heterogeneity and pore size distribution of activated carbons

A new approach based on the nonlocal density functional theory to determine pore size distribution (PSD) of activated carbons and energetic heterogeneity of the pore wall is proposed. The energetic heterogeneity is modeled with an energy distribution function (EDF), describing the distribution of solid-fluid potential well depth (this distribution is a Dirac delta function for an energetic homogeneous surface). The approach allows simultaneous determining of the PSD (assuming slit shape) and EDF from nitrogen or argon isotherms at their respective boiling points by using a set of local isotherms calculated for a range of pore widths and solid-fluid potential well depths. It is found that the structure of the pore wall surface significantly differs from that of graphitized carbon black. This could be attributed to defects in the crystalline structure of the surface, active oxide centers, finite size of the pore walls (in either wall thickness or pore length), and so forth. Those factors depend on the precursor and the process of carbonization and activation and hence provide a fingerprint for each adsorbent. The approach allows very accurate correlation of the experimental adsorption isotherm and leads to PSDs that are simpler and more realistic than those obtained with the original nonlocal density functional theory.

Capillary phenomena in the framework of the two-dimensional density functional theory

We present results of application of the density functional theory (DFT) to adsorption and desorption in finite and infinite cylindrical pores accounting for the density distribution in radial and axial directions. Capillary condensation via formation of bridges is considered using canonical and grand canonical versions of the 2D DFT. The potential barrier of nucleation is determined as a function of the bulk pressure and the pore diameter. In the framework of the conventional assumptions on intermolecular interactions both 1D and 2D DFT versions lead to the same results and confirm the classical scenario of condensation and evaporation: the condensation occurs at the vapor-like spinodal point, and the evaporation corresponds to the equilibrium transition pressure. The analysis of experimental data on argon and nitrogen adsorption on MCM-41 samples seems to not completely corroborate this scenario, with adsorption branch being better described by the equilibrium pressure - diameter dependence. This points to the necessity of the further development of basic representations on the hysteresis phenomena.

Van der Waals-corrected density functional theory: benchmarking for hydrogen-nanotube and nanotube-nanotube interactions

Density functional theory (DFT) is a powerful approach to electronic structure calculations in extended systems, but suffers currently from inadequate incorporation of long-range dispersion, or Van der Waals (VdW) interactions. VdW-corrected DFT is tested for interactions involving molecular hydrogen, graphite, single-walled carbon nanotubes (SWCNTs), and SWCNT bundles. The energy correction, based on an empirical London dispersion term with a damping function at short range, allows a reasonable physisorption energy and equilibrium distance to be obtained for H-2 on a model graphite surface. The VdW-corrected DFT calculation for an (8, 8) nanotube bundle reproduces accurately the experimental lattice constant. For H-2 inside or outside an (8, 8) SWCNT, we find the binding energies are respectively higher and lower than that on a graphite surface, correctly predicting the well known curvature effect. We conclude that the VdW correction is a very effective method for implementing DFT calculations, allowing a reliable description of both short-range chemical bonding and long-range dispersive interactions. The method will find powerful applications in areas of SWCNT research where empirical potential functions either have not been developed, or do not capture the necessary range of both dispersion and bonding interactions.

Modeling of adsorption and nucleation in infinite cylindrical pores by two-dimensional density functional theory

In this paper, we present an analysis of argon adsorption in cylindrical pores having amorphous silica structure by means of a nonlocal density functional theory (NLDFT). In the modeling, we account for the radial and longitudinal density distributions, which allow us to consider the interface between the liquidlike and vaporlike fluids separated by a hemispherical meniscus in the canonical ensemble. The Helmholtz free energy of the meniscus was determined as a function of pore diameter. The canonical NLDFT simulations show the details of density rearrangement at the vaporlike and liquidlike spinodal points. The limits of stability of the smallest bridge and the smallest bubble were also determined with the canonical NLDFT. The energy of nucleation as a function of the bulk pressure and the pore diameter was determined with the grand canonical NLDFT using an additional external potential field. It was shown that the experimentally observed reversibility of argon adsorption isotherms at its boiling point up to the pore diameter of 4 nm is possible if the potential barrier of 22kT is overcome due to density fluctuations.

Self-consistent theory of atomic Fermi gases with a Feshbach resonance at the superfluid transition

A self-consistent theory is derived to describe the BCS-Bose-Einstein-condensate crossover for a strongly interacting Fermi gas with a Feshbach resonance. In the theory the fluctuation of the dressed molecules, consisting of both preformed Cooper pairs and bare Feshbach molecules, has been included within a self-consistent T-matrix approximation, beyond the Nozieres and Schmitt-Rink strategy considered by Ohashi and Griffin. The resulting self-consistent equations are solved numerically to investigate the normal-state properties of the crossover at various resonance widths. It is found that the superfluid transition temperature T-c increases monotonically at all widths as the effective interaction between atoms becomes more attractive. Furthermore, a residue factor Z(m) of the molecule's Green function and a complex effective mass have been determined to characterize the fraction and lifetime of Feshbach molecules at T-c. Our many-body calculations of Z(m) agree qualitatively well with recent measurments of the gas of Li-6 atoms near the broad resonance at 834 G. The crossover from narrow to broad resonances has also been studied.

Adsorption in slit pores and pore-size distribution: A molecular layer structure theory

A new approach is developed to analyze the thermodynamic properties of a sub-critical fluid adsorbed in a slit pore of activated carbon. The approach is based on a representation that an adsorbed fluid forms an ordered structure close to a smoothed solid surface. This ordered structure is modelled as a collection of parallel molecular layers. Such a structure allows us to express the Helmholtz free energy of a molecular layer as the sum of the intrinsic Helmholtz free energy specific to that layer and the potential energy of interaction of that layer with all other layers and the solid surface. The intrinsic Helmholtz free energy of a molecular layer is a function (at given temperature) of its two-dimensional density and it can be readily obtained from bulk-phase properties, while the interlayer potential energy interaction is determined by using the 10-4 Lennard-Jones potential. The positions of all layers close to the graphite surface or in a slit pore are considered to correspond to the minimum of the potential energy of the system. This model has led to accurate predictions of nitrogen and argon adsorption on carbon black at their normal boiling points. In the case of adsorption in slit pores, local isotherms are determined from the minimization of the grand potential. The model provides a reasonable description of the 0-1 monolayer transition, phase transition and packing effect. The adsorption of nitrogen at 77.35 K and argon at 87.29 K on activated carbons is analyzed to illustrate the potential of this theory, and the derived pore-size distribution is compared favourably with that obtained by the Density Functional Theory (DFT). The model is less time-consuming than methods such as the DFT and Monte-Carlo simulation, and most importantly it can be readily extended to the adsorption of mixtures and capillary condensation phenomena.

Validation of the Action Research Arm Test using item response theory in patients after stroke

Objective: To validate the unidimensionality of the Action Research Arm Test (ARAT) using Mokken analysis and to examine whether scores of the ARAT can be transformed into interval scores using Rasch analysis. Subjects and methods: A total of 351 patients with stroke were recruited from 5 rehabilitation departments located in 4 regions of Taiwan. The 19-item ARAT was administered to all the subjects by a physical therapist. The data were analysed using item response theory by non-parametric Mokken analysis followed by Rasch analysis. Results: The results supported a unidimensional scale of the 19-item ARAT by Mokken analysis, with the scalability coefficient H = 0.95. Except for the item pinch ball bearing 3rd finger and thumb'', the remaining 18 items have a consistently hierarchical order along the upper extremity function's continuum. In contrast, the Rasch analysis, with a stepwise deletion of misfit items, showed that only 4 items (grasp ball'', grasp block 5 cm(3)'', grasp block 2.5 cm(3)'', and grip tube 1 cm(3)'') fit the Rasch rating scale model's expectations. Conclusion: Our findings indicated that the 19-item ARAT constituted a unidimensional construct measuring upper extremity function in stroke patients. However, the results did not support the premise that the raw sum scores of the ARAT can be transformed into interval Rasch scores. Thus, the raw sum scores of the ARAT can provide information only about order of patients on their upper extremity functional abilities, but not represent each patient's exact functioning.

Dartboard arrangements with a concave penalty function

This paper investigates combinatorial arrangements of the dartboard to maximize a penalty function derived from the differences of adjacent sectors. The particular penalty function is constructed by summing the absolute differences of neighbouring sectors raised to a power between zero and one. The arrangement to give the maximum penalty is found

A linguistic and semantic approach to the theory and practice of literary translation

This work explores the relevance of semantic and linguistic description to translation, theory and practice. It is aimed towards a practical model of approach to texts to translate. As literary texts [poetry mainly] are the focus of attention, so are stylistic matters. Note, however, that 'style', and, to some extent, the conclusions of the work, are not limited to so-called literary texts. The study of semantic description reveals that most translation problems do not stem from the cognitive (langue-related), but rather from the contextual (parole-related) aspects of meaning. Thus, any linguistic model that fails to account for the latter is bound to fall short. T.G.G. does, whereas Systemics, concerned with both the 'Iangue' and 'parole' (stylistic and sociolinguistic mainly) aspects of meaning, provides a useful framework of approach to texts to translate. Two essential semantic principles for translation are: that meaning is the property of a language (Firth); and the 'relativity of meaning assignments' (Tymoczko). Both imply that meaning can only be assessed, correctly, in the relevant socio-cultural background. Translation is seen as a restricted creation, and the translator's encroach as a three-dimensional critical one. To encompass the most technical to the most literary text, and account for variations in emphasis in any text, translation theory must be based on typology of function Halliday's ideational, interpersonal and textual, or, Buhler's symbol, signal, symptom, Functions3. Function Coverall and specific] will dictate aims and method, and also provide the critic with criteria to assess translation Faithfulness. Translation can never be reduced to purely objective methods, however. Intuitive procedures intervene, in textual interpretation and analysis, in the choice of equivalents, and in the reception of a translation. Ultimately, translation, theory and practice, may perhaps constitute the touchstone as regards the validity of linguistic and semantic theories.

Transducer diffraction theory and development of an ultrasonic tomogram

The work described in this thesis is the development of an ultrasonic tomogram to provide outlines of cross-sections of the ulna in vivo. This instrument, used in conjunction with X-ray densitometry previously developed in this department, would provide actual bone mineral density to a high resolution. It was hoped that the accuracy of the plot obtained from the tomogram would exceed that of existing ultrasonic techniques by about five times. Repeat measurements with these instruments to follow bone mineral changes would involve very low X-ray doses. A theoretical study has been made of acoustic diffraction, using a geometrical transform applicable to the integration of three different Green's functions, for axisymmetric systems. This has involved the derivation of one of these in a form amenable to computation. It is considered that this function fits the boundary conditions occurring in medical ultrasonography more closely than those used previously. A three dimensional plot of the pressure field using this function has been made for a ring transducer, in addition to that for disc transducers using all three functions. It has been shown how the theory may be extended to investigate the nature and magnitude of the particle velocity, at any point in the field, for the three functions mentioned. From this study. a concept of diffraction fronts has been developed, which has made it possible to determine energy flow also in a diffracting system. Intensity has been displayed in a manner similar to that used for pressure. Plots have been made of diffraction fronts and energy flow direction lines.

Oculomotor function in incipient presbyopia

The incipient phase of presbyopia represents a loss in accommodative amplitude of approximately 3 dioptres between the ages of 35 and 45 and is the prelude to the need for a reading addition. The need to maintain single binocular vision during this period requires re-calibration of the correspondence between accommodation and vergence response. No previous study has specifically attempted to correlate change in accommodative status with the profile of oculomotor responses occurring within the incipient phase of presbyopia. Measurements were made of the amplitude of accommodation, stimulus and response AC/A ratios, CA/C ratio, tonic accommodation, tonic vergence, proximal vergence, vergence adaptation and accommodative adaptation of 38 subjects. Twenty subjects were aged 35 to 45 years of age and 10 subjects were aged 20 to 30 years of age at the commencement of the study. The measurements were repeated at four-monthly intervals for a total of two years. The results of this study fail to support the Hess-Gullstrand theory of presbyopia with evidence that the effort to produce a unit change in accommodation increases with age. The data obtained has enabled the analysis of how each individual oculomotor function varies with the decline in amplitude of accommodation. MATLAB/SIMULINK software has been used to assist in the analysis and to allow the amendment of existing models to represent accurately the ageing oculomotor system. This study has proposed that with the decline in the amplitude of accommodation there is an increase in the accommodative convergence response per unit of accommodative response. To compensate for this increase, evidence has been found of a decrease in tonic vergence with age. If this decline in tonic vergence is not sufficient to counteract the increase in accommodative convergence, it is proposed that the near vision response is limited to the maximum vergence response that can be tolerated, with the resulting lower accommodative response being compensated for by an increase in the subjective depth-of-focus. When the blur due to the decrease in accommodative response can no longer be tolerated, the first reading addition will be required.

Theory and data for area summation of contrast with and without uncertainty:evidence for a noisy energy model

Contrast sensitivity improves with the area of a sine-wave grating, but why? Here we assess this phenomenon against contemporary models involving spatial summation, probability summation, uncertainty, and stochastic noise. Using a two-interval forced-choice procedure we measured contrast sensitivity for circular patches of sine-wave gratings with various diameters that were blocked or interleaved across trials to produce low and high extrinsic uncertainty, respectively. Summation curves were steep initially, becoming shallower thereafter. For the smaller stimuli, sensitivity was slightly worse for the interleaved design than for the blocked design. Neither area nor blocking affected the slope of the psychometric function. We derived model predictions for noisy mechanisms and extrinsic uncertainty that was either low or high. The contrast transducer was either linear (c1.0) or nonlinear (c2.0), and pooling was either linear or a MAX operation. There was either no intrinsic uncertainty, or it was fixed or proportional to stimulus size. Of these 10 canonical models, only the nonlinear transducer with linear pooling (the noisy energy model) described the main forms of the data for both experimental designs. We also show how a cross-correlator can be modified to fit our results and provide a contemporary presentation of the relation between summation and the slope of the psychometric function.

The propensity to disrupt and the disruption nucleolus of a characteristic function game

Gately [1974] recently introduced the concept of an individual player's “propensity to disrupt” a payoff vector in a three-person characteristic function game. As a generalisation of this concept we propose the “disruption nucleolus” of ann-person game. The properties and computational possibilities of this concept are analogous to those of the nucleolus itself. Two numerical examples are given.