Defect free energy

To our knowledge there have been no reported measurements of equilibrium defect concentrations in soft-sphere models. Similarly, relatively few measurements have been reported of defect free energies in models for real systems. Those that exist rely on integration methods to connect the defective solid to the perfect solid. In ab initio studies the computational cost of this procedure can be high, although results have recently started to appear, most notably for vacancies and interstitial defects in silicon. For a review see Ref. 109. 

A fully microscopic interpretation of the temperature dependence of the absorption maximum, even well above any order-disorder transition temperature, is a formidable task because of the potential importance of many complicated physical factors (27-30). As a first attack on this problem, we have adopted a simple mean-field (or effective-medium) approach (28-30) with the assumption that the absorption peak (to) is linearly perturbed from its limiting dl -trans value ((Orod) by the presence of bond rotational defects (free energy of formation, e)... 

Atomistic simulations can be used to estimate defect free energies which can then be used as input parameters in thermodynamic models for copolymer crystallization. Recent work by Wendling et al [167-170] has demonstrated the utility of this combined approach conclusively. It is anticipated that such investigations will become increasingly more common in the future. 

Consider the case where the substrate is perturbed in a periodic manner in the y direction. In a region of size D in the vicinity of each defect, the substrate is perturbed with a strength wq and is unperturbed outside that region. Using Eq. (4.38) and the appropriate representation of the defect free energy, calculate the displacement of the contact line at x = 0. 

In a defect-free, undoped, semiconductor, tliere are no energy states witliin tire gap. At 7"= 0 K, all of tire VB states are occupied by electrons and all of the CB states are empty, resulting in zero conductivity. The tliennal excitation of electrons across tire gap becomes possible at T > 0 and a net electron concentration in tire CB is established. The electrons excited into tire CB leave empty states in tire VB. These holes behave like positively charged electrons. Botli tire electrons in the CB and holes in tire VB participate in tire electrical conductivity. 

Four Challenges in IVIoSecula Modelling Free Energies, Solvation, Reactions and Solid-state Defects... 

In this chapter we shall consider four important problems in molecular n iudelling. First, v discuss the problem of calculating free energies. We then consider continuum solve models, which enable the effects of the solvent to be incorporated into a calculation witho requiring the solvent molecules to be represented explicitly. Third, we shall consider the simi lation of chemical reactions, including the important technique of ab initio molecular dynamic Finally, we consider how to study the nature of defects in solid-state materials. 

The most direct effect of defects on tire properties of a material usually derive from altered ionic conductivity and diffusion properties. So-called superionic conductors materials which have an ionic conductivity comparable to that of molten salts. This h conductivity is due to the presence of defects, which can be introduced thermally or the presence of impurities. Diffusion affects important processes such as corrosion z catalysis. The specific heat capacity is also affected near the melting temperature the h capacity of a defective material is higher than for the equivalent ideal crystal. This refle the fact that the creation of defects is enthalpically unfavourable but is more than comp sated for by the increase in entropy, so leading to an overall decrease in the free energy... 

The effect of different types of comonomers on varies. VDC—MA copolymers mote closely obey Flory s melting-point depression theory than do copolymers with VC or AN. Studies have shown that, for the copolymers of VDC with MA, Flory s theory needs modification to include both lamella thickness and surface free energy (69). The VDC—VC and VDC—AN copolymers typically have severe composition drift, therefore most of the comonomer units do not belong to crystallizing chains. Hence, they neither enter the crystal as defects nor cause lamellar thickness to decrease, so the depression of the melting temperature is less than expected. 

In pure and stoichiometric compounds, intrinsic defects are formed for energetic reasons. Intrinsic ionic conduction, or creation of thermal vacancies by Frenkel, ie, vacancy plus interstitial lattice defects, or by Schottky, cation and anion vacancies, mechanisms can be expressed in terms of an equilibrium constant and, therefore, as a free energy for the formation of defects, If the ion is to jump into a normally occupied lattice site, a term for... 

Nucleation in solids is very similar to nucleation in liquids. Because solids usually contain high-energy defects (like dislocations, grain boundaries and surfaces) new phases usually nucleate heterogeneously homogeneous nucleation, which occurs in defect-free regions, is rare. Figure 7.5 summarises the various ways in which nucleation can take place in a typical polycrystalline solid and Problems 7.2 and 7.3 illustrate how nucleation theory can be applied to a solid-state situation. 

To illustrate yet one approach to analysis of defect formation, consider the influence of Br2 gas upon defect formation in AgBr. The free energy of formation, AG, is related to the reaction ... 

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