Direct calculation of ionization energies

The advantages of the propagator formalism, as a direct method of calculating ionization energies, are stressed. The propagator equations are derived for closed-shell systems using an operator method instead of the usual diagrammatic derivations. The equations enable the development of an interpretation of the ionization energies in terms of conceptually simple quantities, such as pair correlation energies and associated relaxation effects, and retain the idea of orbital ionization. Infinite summations appearing in the self-energy terms are replaced by finite expressions involving functions satisfying uncoupled inhomogeneous differential equations. Certain high-order propagator equations are derived, and a connection with the Bethe-Goldstone formulation of pair correlation is made. Several computational procedures are advocated as forming the basis for balanced calculations of atomic and molecular ionization energies.     

Identification of geometric parameters influencing the flow-induced vibration of a two-layer self-oscillating computational vocal fold model

Simplified models have been used to simulate and study the flow-induced vibrations of the human vocal folds. While it is clear that the models' responses are sensitive to geometry, it is not clear how and to what extent specific geometric features influence model motion. In this study geometric features that played significant roles in governing the motion of a two-layer (body-cover), two-dimensional, finite element vocal fold model were identified. The model was defined using a flow solver based on the viscous, unsteady, Navier-Stokes equations and a solid solver that allowed for large strain and deformation. A screening-type design-of-experiments approach was used to identify the relative importance of 13 geometric parameters. Five output measures were analyzed to assess the magnitude of each geometric parameter's effect on the model's motion. The measures related to frequency, glottal width, flow rate, intraglottal angle, and intraglottal phase delay. The most significant geometric parameters were those associated with the cover--primarily the pre-phonatory intraglottal angle--as well as the body inferior angle. Some models exhibited evidence of improved model motion, including mucosal wave-like motion and alternating convergent-divergent glottal profiles, although further improvements are still needed to more closely mimic human vocal fold motion.     

Multi-Stage Upscaling: Selection of Suitable Methods

Reservoirs are often composed of an assortment of rock types giving rise to permeability heterogeneities at a variety of length-scales. To predict fluid flow at the full-field scale, it is necessary to be aware of these different types of heterogeneity, to recognise which are likely to have important effects on fluid flow, and to capture them by upscaling. In fact, we may require a series of stages of upscaling to go from small-scales (mm or cm) to a full-field model. When there are two (or more) phases present, we also need to know how these heterogeneities interact with fluid forces (capillary, viscous and gravity). We discuss how these effects may be taken into account by upscaling. This study focusses on the effects of steady-state upscaling for viscous-dominated floods and tests carried out on a range of 2D models are described. Upscaling errors are shown to be reduced slightly by the increase in numerical dispersion at the coarse scale. We select a combination of three different upscaling methods, and apply this approach to a model of a North Sea oil reservoir in a deep marine environment. Six different genetic units (rock types) were identified, including channel sandstone and inter-bedded sandstone and mudstone. These units were modelled using different approaches, depending on the nature of the heterogeneities. Our results show that the importance of small-scale heterogeneity depends on the large-scale distribution of the rock types. Upscaling may not be worthwhile in sparsely distributed genetic units. However, it is important in the dominant rock type, especially if there is good connectivity through the unit between the injector wells (or aquifer) and the producer wells.This revised version was published online in May 2005. In the previous version one of the authors name was missing.     

The Development of Appropriate Upscaling Procedures

Permeability upscaling should be carried out with careful attention to the nature of rock heterogeneities. While there are many large-scale features which must be taken into account, there are also important heterogeneities at the small-scale. Many sedimentary structures contain laminae at the mm–cm scale, and beds at the m-scale, which give rise to strong contrasts in permeability. We use a 2D model derived from a photo-panel of an aeolian outcrop, along with permeability measurements from a North Sea oil field, to demonstrate the effects of small-scale heterogeneity. This model is similar in size to a typical cell of a reservoir geological model. We take imaginary probe and core plug measurements from the model, average them, and compare these with the effective permeability for the model computed from a finite difference flow calculation. Although this procedure is standard practice, we show that it can lead to biased estimates of the permeabilities used in flow simulation. As an alternative we suggest using models of representative beds, and performing flow simulation to calculate effective permeabilities for both single-phase and two-phase flow.     

Charging and discharging rate studies of polypyrrole films in AlCl3: 1-methyl-(3-ethyl)-imidazolium chloride molten salts and in CH3CN

The chronocoulometric charging and discharging of polypyrrole films in basic AlCl₃/1-methyl-(3-ethyl)-imidazolium chloride molten salts and CH₃CN have been investigated. Both processes follow a t^{$\text{1}\text{2}$} time dependence and are significantly faster in the molten salts. Comparison with redox polymer and porous electrode models shows that neither model is satisfactorily applicable over the entire potential region studied. The charging and discharging rates are limited by ion migration in the polymer and for potential steps in the “double layer charging” region polypyrrole behaves as a porous electrode material. In this region there is a good correlation between the charging/discharging rates and the solvent conductivity.     

Non-planar smoulder propagation governed by diffusion

The steady propagation of a thin smouldering front in a half-spacehas been considered. A suitable coordinate transformation hasallowed the region near the leading edge of the front to beexamined for both a maintained planar surface and with surfacecollapse due to material shrinkage. The change in the oxidizerconcentration for a small increment in the propagation speedfor large time and surface collapse has been determined. Theinfluence of two types of nonlinear diffusion on the shape ofthe smouldering front has been found; other cases can be dealtwith in a similar manner.     

Extended Koopmans' theorem and sudden ionization processes

The extended Koopmans' theorem eigenvalues of a correlated ground state are shown to represent the centroids of groups of ionization processes in the sudden limit. Lowest order relaxation effects are absent.     

On a field-theoretic formulation of many-electron spin-adaptation

We report the development of a set of spin-adapted creation and annihilation operators which provides a suitable generalisation of the usual many-body apparatus.     

Characterisation of sol-gel prepared (HfO2)x(SiO2)1-x (x=0.1, 0.2 and 0.4) by 1H, 13C, 17 O and 29Si MAS NMR, FTIR and TGA

The HfO2-SiO2 system is attracting interest as a possible new dielectric material in semiconductor devices. Knowledge of the location of hafnium within the silica network and the effect hafnium has on the structure will be central to the successful use of this material system in this application. Here, sol-gel techniques have been used to manufacture (HfO2)x(SiO2)1-x samples (x=0.1, 0.2 and 0.4, each heat treated at 250, 500 and 750 degrees C) and these have been characterised by magic angle spinning (MAS) NMR (1H, 13C, 17 O, 29Si), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. 29Si MAS NMR showed that increasing the hafnia content decreases the connectivity of the silicate network, i.e. increases the range of differently connected SiO4 (Qn) units with more having increased numbers of non-bridging oxygens (i.e. lower n). FTIR and 17 O MAS NMR showed unequivocally that the x=0.4 sample phase-separated at higher temperatures, while in the x=0.1 sample the hafnium was homogeneously mixed into the SiO2 phase without any phase separation.