Mean theory

One should be aware of the limitations of the Landau theory, chief of which are the fact that it can be applied only where the expansion of in a limited power series in rj is tenable also, in common with all other mean theories, fluctuation effects have not been taken into account. 

Interfadal tension between two fluid phases is a definite and accurately measurable property depending on the properties of both phases. Also, the contact angle, depending now on the properties of the three phases, is an accurately measurable property. Experimental approaches are described, e.g., in Refs. 8,60, and 63 and in Ref. 62, where especially detailed discussion of the Wilhehny technique is presented. Theories such as harmonic mean theory, geometric mean theory, and acid base theory (reviewed, e.g., in Refs. 8, 20, and 64) allow calculation of the soHd surface energy (because it is difficult to directly measure) from the contact angle measurements with selected test liquids with known surface tension values. These theories require introduction of polar and dispersive components of the surface free energy. 

In more recent work by Shull and coworkers, the preparation of swollen micelle composites was investigated using self-consistent mean theory (Lefebvre and Shull, 2006). This theoretical approach concluded that nanoparticles can be encapsulated in the center of swollen micelles by including an external-field term that creates an attraction between the surface of the particle and the homopolymer. This predicts the formation of nanocomposites from a diblock copolymer (AB) and additional selectively attractive homopolymer (C). This is achieved by first preparing a layer of C homopolymer, then a layer of nanoparticles, and then a blend of A homopolymer and asymmetric AB copolymer. Then upon annealing, favorable interactions between B and C repeat units cause the copolymer to migrate to the A/C interface. Attraction between the particle and the C repeat units causes the particles to diffuse into the C phase. When the interfacial tension is lowered by the copolymer, the interface develops curvature and micelles swollen with C form around the particles in the A phase. 

In statistical mechanics (e.g. the theory of specific heats of gases) a degree of freedom means an independent mode of absorbing energy by movement of atoms. Thus a mon-... 

The capillary rise method is generally considered to be the most accurate means to measure 7, partly because the theory has been worked out with considerable exactitude and partly because the experimental variables can be closely controlled. This is to some extent a historical accident, and other methods now rival or surpass the capillary rise one in value. 

A related approach carries out lattice sums using a suitable interatomic potential, much as has been done for rare gas crystals [82]. One may also obtain the dispersion component to E by estimating the Hamaker constant A by means of the Lifshitz theory (Eq. VI-30), but again using lattice sums [83]. Thus for a FCC crystal the dispersion contributions are... 

Density functional theory from statistical mechanics is a means to describe the thermodynamics of the solid phase with information about the fluid [17-19]. In density functional theory, one makes an ansatz about the structure of the solid, usually describing the particle positions by Gaussian distributions around their lattice sites. The free... 

The entropically driven disorder-order transition in hard-sphere fluids was originally discovered in computer simulations [58, 59]. The development of colloidal suspensions behaving as hard spheres (i.e., having negligible Hamaker constants, see Section VI-3) provided the means to experimentally verify the transition. Experimental data on the nucleation of hard-sphere colloidal crystals [60] allows one to extract the hard-sphere solid-liquid interfacial tension, 7 = 0.55 0.02k T/o, where a is the hard-sphere diameter [61]. This value agrees well with that found from density functional theory, 7 = 0.6 0.02k r/a 2 [21] (Section IX-2A). 

The behavior of insoluble monolayers at the hydrocarbon-water interface has been studied to some extent. In general, a values for straight-chain acids and alcohols are greater at a given film pressure than if spread at the water-air interface. This is perhaps to be expected since the nonpolar phase should tend to reduce the cohesion between the hydrocarbon tails. See Ref. 91 for early reviews. Takenaka [92] has reported polarized resonance Raman spectra for an azo dye monolayer at the CCl4-water interface some conclusions as to orientation were possible. A mean-held theory based on Lennard-Jones potentials has been used to model an amphiphile at an oil-water interface one conclusion was that the depth of the interfacial region can be relatively large [93]. 

It will be seen that each method for surface area determination involves the measurement of some property that is observed qualitatively to depend on the extent of surface development and that can be related by means of theory to the actual surface area. It is important to realize that the results obtained by different methods differ, and that one should in general expect them to differ. The problem is that the concept of surface area turns out to be a rather elusive one as soon as it is examined in detail. 

The subject of gas adsorption is, indeed, a very broad one, and no attempt is made to give complete coverage to the voluminous literature on it. Instead, as in past chapters, the principal models or theories are taken up partly for their own sake and partly as a means of introducing characteristic data. 

The Langmuir-Hinshelwood picture is essentially that of Fig. XVIII-14. If the process is unimolecular, the species meanders around on the surface until it receives the activation energy to go over to product(s), which then desorb. If the process is bimolecular, two species diffuse around until a reactive encounter occurs. The reaction will be diffusion controlled if it occurs on every encounter (see Ref. 211) the theory of surface diffusional encounters has been treated (see Ref. 212) the subject may also be approached by means of Monte Carlo/molecular dynamics techniques [213]. In the case of activated bimolecular reactions, however, there will in general be many encounters before the reactive one, and the rate law for the surface reaction is generally written by analogy to the mass action law for solutions. That is, for a bimolecular process, the rate is taken to be proportional to the product of the two surface concentrations. It is interesting, however, that essentially the same rate law is obtained if the adsorption is strictly localized and species react only if they happen to adsorb on adjacent sites (note Ref. 214). (The apparent rate law, that is, the rate law in terms of gas pressures, depends on the form of the adsorption isotherm, as discussed in the next section.)... 

The result is that, to a very good approxunation, as treated elsewhere in this Encyclopedia, the nuclei move in a mechanical potential created by the much more rapid motion of the electrons. The electron cloud itself is described by the quantum mechanical theory of electronic structure. Since the electronic and nuclear motion are approximately separable, the electron cloud can be described mathematically by the quantum mechanical theory of electronic structure, in a framework where the nuclei are fixed. The resulting Bom-Oppenlieimer potential energy surface (PES) created by the electrons is the mechanical potential in which the nuclei move. Wlien we speak of the internal motion of molecules, we therefore mean essentially the motion of the nuclei, which contain most of the mass, on the molecular potential energy surface, with the electron cloud rapidly adjusting to the relatively slow nuclear motion. 

Geometrically, Liouville s theorem means that if one follows the motion of a small phase volume in Y space, it may change its shape but its volume is invariant. In other words the motion of this volume in T space is like that of an incompressible fluid. Liouville s theorem, being a restatement of mechanics, is an important ingredient in the fomuilation of the theory of statistical ensembles, which is considered next. 

Although the exact equations of state are known only in special cases, there are several usefid approximations collectively described as mean-field theories. The most widely known is van der Waals equation [2]... 

The parameters a and b are characteristic of the substance, and represent corrections to the ideal gas law dne to the attractive (dispersion) interactions between the atoms and the volnme they occupy dne to their repulsive cores. We will discnss van der Waals equation in some detail as a typical example of a mean-field theory. 

This is the well known equal areas mle derived by Maxwell [3], who enthusiastically publicized van der Waal s equation (see figure A2.3.3. The critical exponents for van der Waals equation are typical mean-field exponents a 0, p = 1/2, y = 1 and 8 = 3. This follows from the assumption, connnon to van der Waals equation and other mean-field theories, that the critical point is an analytic point about which the free energy and other themiodynamic properties can be expanded in a Taylor series. 

The thennodynamic properties of a fluid can be calculated from the two-, tln-ee- and higher-order correlation fiinctions. Fortunately, only the two-body correlation fiinctions are required for systems with pairwise additive potentials, which means that for such systems we need only a theory at the level of the two-particle correlations. The average value of the total energy... 

Table A2.3.4 simnnarizes the values of these critical exponents m two and tliree dimensions and the predictions of mean field theory.

As a prelude to discussing mean-field theory, we review the solution for non-interacting magnets by setting J = 0 in the Ising Flamiltonian. The PF... 

Fluctuations in the magnetization are ignored by mean-field theory and there is no correlation between neighbouring sites, so that... 

The neglect of fluctuations in mean-field theory implies that... 

Table A2.3.5 Critical temperatures predicted by mean-field theory (MFT) and the quasi-chemical (QC) approximation compared with the exact results.

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