Model ellipsoidal

Reaction no. t Parent compound0 Solvent W/io M s l /Up / kcal mol Spherical model" Ellipsoidal model" r calc/ A Ref. 

The simplest reaction field model, known as the Born model, consists of a spherical cavity where only the net charge and the dipole moment of the molecule are considered. When the solute is represented by a set of atomic charges the model is often called Generalized Born (GB) Model. Ellipsoidal cavities can also be employed as in the early Kirkwood-Westheimer model. The main advantage of these simple models is that [Eq. (7.12)] can be computed analytically. Unfortunately, they are of limited accuracy. 

For molecules of this shape, the isotropic phase is found to undergo a transition directly into the biaxial phase on compression. A biaxial phase has also been observed in simulations of mixtures of rods and platelets, in which the different species are modelled ellipsoids with aspect ratios of x = 20 and X = 1/20, respectively [19]. However, here the range of the biaxial phase is severely limited by demixing into two coexisting uniaxial nematics, one rich in rods, the other rich in discs. 

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

The spherical shell model can only account for tire major shell closings. For open shell clusters, ellipsoidal distortions occur [47], leading to subshell closings which account for the fine stmctures in figure C1.1.2(a ). The electron shell model is one of tire most successful models emerging from cluster physics. The electron shell effects are observed in many physical properties of tire simple metal clusters, including tlieir ionization potentials, electron affinities, polarizabilities and collective excitations [34]. 

It has not proved possible to develop general analytical hard-core models for liquid crystals, just as for nonnal liquids. Instead, computer simulations have played an important role in extending our understanding of the phase behaviour of hard particles. Frenkel and Mulder found that a system of hard ellipsoids can fonn a nematic phase for ratios L/D >2.5 (rods) or L/D <0.4 (discs) [73] however, such a system cannot fonn a smectic phase, as can be shown by a scaling... 

The early Hartley model [2, 3] of a spherical micellar stmcture resulted, in later years, in some considerable debate. The self-consistency (inconsistency) of spherical symmetry witli molecular packing constraints was subsequently noted [4, 5 and 6]. There is now no serious question of tlie tenet tliat unswollen micelles may readily deviate from spherical geometry, and ellipsoidal geometries are now commonly reported. Many micelles are essentially spherical, however, as deduced from many light and neutron scattering studies. Even ellipsoidal objects will appear... 

In addition to an array of experimental methods, we also consider a more diverse assortment of polymeric systems than has been true in other chapters. Besides synthetic polymer solutions, we also consider aqueous protein solutions. The former polymers are well represented by the random coil model the latter are approximated by rigid ellipsoids or spheres. For random coils changes in the goodness of the solvent affects coil dimensions. For aqueous proteins the solvent-solute interaction results in various degrees of hydration, which also changes the size of the molecules. Hence the methods we discuss are all potential sources of information about these interactions between polymers and their solvent environments. 

Fig. 13. Model of the growth of a nanotubule bonded to the catalyst surface, (a) Growth of a straight (5,5) nanotubule on a catalyst particle, with perimeter I5ak (b) growth of a straight (9,0) nanotubule on a catalyst particle whose perimeter is 18ak (k is a constant and the grey ellipsoids of (a) and (b) represent catalyst particles, the perimeters of which are equal to 5ak and 18a/t, respectively) (c) (5,5)-(9,0) knee, the two sides should grow optimally on catalyst particles having perimeters differing by ca. 20%.

In this review we consider several systems in detail, ranging from idealized models for adsorbates with purely repulsive interactions to the adsorption of spherical particles (noble gases) and/or (nearly) ellipsoidal molecules (N2, CO). Of particular interest are the stable phases in monolayers and the phase transitions between these phases when the coverage and temperature in the system are varied. Most of the phase transitions in these systems occur at fairly low temperatures, and for many aspects of the behavior quantum effects need to be considered. For several other theoretical studies of adsorbed layer phenomena see Refs. 59-89. 

A similar acoustic technique was applied by Pickles and Bittleston (1983) to investigate blast produced by an elongated, or cigar-shaped, cloud. The cloud was modeled as an ellipsoid with an aspect ratio of 10. The explosion was simulated by a continuous distribution of volume sources along the main axis with a strength proportional to the local cross-sectional area of the ellipsoid. The blast produced by such a vapor cloud explosion was shown to be highly directional along the main axis. 

The simplest shape for the cavity is a sphere or possibly an ellipsoid. This has the advantage that the electrostatic interaction between M and the dielectric medium may be calculated analytically. More realistic models employ moleculai shaped cavities, generated for example by interlocking spheres located on each nuclei. Taking the atomic radius as a suitable factor (typical value is 1.2) times a van der Waals radius defines a van der Waals surface. Such a surface may have small pockets where no solvent molecules can enter, and a more appropriate descriptor may be defined as the surface traced out by a spherical particle of a given radius rolling on the van der Waals surface. This is denoted the Solvent Accessible Surface (SAS) and illustrated in Figm e 16.7. 

The spherical cavity, dipole only, SCRF model is known as the OnMger model.The Kirkwood model s refers to a general multipole expansion, if the cavity is ellipsoidal the Kirkwood—Westheimer model arise." A fixed dipole moment of yr in the Onsager model gives rise to an energy stabilization. 

In connection with electronic strucmre metlrods (i.e. a quantal description of M), the term SCRF is quite generic, and it does not by itself indicate a specific model. Typically, however, the term is used for models where the cavity is either spherical or ellipsoidal, the charge distribution is represented as a multipole expansion, often terminated at quite low orders (for example only including the charge and dipole terms), and the cavity/ dispersion contributions are neglected. Such a treatment can only be used for a qualitative estimate of the solvent effect, although relative values may be reasonably accurate if the molecules are fairly polar (dominance of the dipole electrostatic term) and sufficiently similar in size and shape (cancellation of the cavity/dispersion terms). 

The representation of the dispersion viscosity given above related to suspensions of particles of spherical form. Upon a transition to anisodiametrical particles a number of new effects arises. The effect of nonsphericity is often discussed on the example of model dispersions of particles of ellipsoidal form. An exact form of particles to a first approximation is not very significant, the degree of anisodiametricity is only important, or for ellipsoidal-particles, their eccentricity. 

The close-packed-spheron theory8 incorporates some of the features of the shell model, the alpha-particle model, and the liquid-drop model. Nuclei are considered to be close-packed aggregates of spherons (helicons, tritons, and dineutrons), arranged in spherical or ellipsoidal layers, which are called the mantle, the outer core, and the inner core. The assignment of spherons, and hence nucleons, to the layers is made in a straightforward way on... 

An ellipsoidal nucleus with two spherons in the inner core has major radius greater than the minor radii by the radius of a spheron. about 1.5 f, which is about 25 percent of the mean radius. The amount of deformation given by this model is accordingly in rough agreement with that observed (18). In a detailed treatment it would be necessary to take into account the effect of electrostatic repulsion in causing the helions to tend to occupy the poles of the prolate mantle, with tritons tending to the equator. 

In simple single-site liquid crystal models, such as hard-ellipsoids or the Gay-Berne potential, a number of elegant techniques have been devised to calculate key bulk properties which are useful for display applications. These include elastic constants for nematic systems [87, 88]. However, these techniques are dependent on large systems and long runs, and (at the present time) limitations in computer time prevent the extension of these methods to fully atomistic models. 

The implementation of this formalism for an atomistic model does not present any difficulties, at least conceptually. However, it is not obvious how the formalism should be used for single site potentials such as the Gay-Berne model. One approach would be to superimpose a mesogenic structure on the Gay-Berne ellipsoid but this structure would necessarily have a lower symmetry. Alternatively it would be possible to place a line of atoms along... 

There have been several simulations of discotic liquid crystals based on hard ellipsoids [41], infinitely thin platelets [59, 60] and cut-spheres [40]. The Gay-Berne potential model was then used to simulate the behaviour of discotic systems by Emerson et al. [16] in order to introduce anisotropic attractive forces. In this model the scaled and shifted separation R (see Eq. 5) was given by... 

Sanchez, C. Schmitt, C. Kolodziejczyk, E. Lapp, A. Gaillard, C. Renard, D. (2008). The Acacia Gum Arabinogalactan Fraction Is a Thin Oblate Ellipsoid A New Model Based on Small-Angle Neutron Scattering and Ab Initio Calculation. Biophysical Journal, Vol. 94, No. 2, (January 2008), pp.629-639, ISSN 0006-3495. 

For linear models the joint confidence region is an Alp-dimensional ellipsoid. All parameters encapsulated within this hyperellipsoid do not differ significantly from the optimal estimates at the probability level of 1-a. 

Determination of confidence limits for non-linear models is much more complex. Linearization of non-linear models by Taylor expansion and application of linear theory to the truncated series is usually utilized. The approximate measure of uncertainty in parameter estimates are the confidence limits as defined above for linear models. They are not rigorously valid but they provide some idea about reliability of estimates. The joint confidence region for non-linear models is exactly given by Eqn. (B-34). Contrary to ellipsoidal contours for linear models it is generally banana-shaped. 

In three dimensions (Fig. 33.5), the model takes the shape of an ellipsoid and in m dimensions, we must imagine an rn-dimensional hyperellipsoid. In the figure, two classes are considered and we now observe that four situations can be encountered when classifying an object, namely ... 

Radial basis function networks (RBF) are a variant of three-layer feed forward networks (see Fig 44.18). They contain a pass-through input layer, a hidden layer and an output layer. A different approach for modelling the data is used. The transfer function in the hidden layer of RBF networks is called the kernel or basis function. For a detailed description the reader is referred to references [62,63]. Each node in the hidden unit contains thus such a kernel function. The main difference between the transfer function in MLF and the kernel function in RBF is that the latter (usually a Gaussian function) defines an ellipsoid in the input space. Whereas basically the MLF network divides the input space into regions via hyperplanes (see e.g. Figs. 44.12c and d), RBF networks divide the input space into hyperspheres by means of the kernel function with specified widths and centres. This can be compared with the density or potential methods in pattern recognition (see Section 33.2.5). 

Approximate inference regions for nonlinear models are defined by analogy to the linear models. In particular, the (I-a)I00% joint confidence region for the parameter vector k is described by the ellipsoid,... 

Figure 4 demonstrates the results of several investigations. It can be seen that both methods lead to a linear dependence between c and Mw but differ by a factor of ten. The reason is seen in the fact that c ] depends on a model (Einstein s law), whereas c LS gives absolute results. In both cases the geometric shape of the polymer coils are assumed to be spherical but, in accordance with the findings of Kuhn, we know that the most probable form can be best represented as a bean-like (irregularly ellipsoidal) structure. 

Figure 4.16 Double bond (a) Lewis model of two tetrahedra sharing an edge, (b) Domain model the two single electron pair domains of the double bond are pulled in toward each other by the attraction of the two carbon cores forming one four-electron double-bond domain with a prolate ellipsoidal shape, thereby allowing the two hydrogen ligands to move apart.

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