Interfaces phenomenology

According to Gibbs [1], one can view an interface as a layer of finite thickness within which the composition and thermodynamic characteristics are different from those in the bulk of phases in contact. This approach allows one to describe the properties of interfaces phenomenologically in terms of excesses of the thermodynamic functions in the interfacial layer in comparison with the bulk of individual phases. With this approach one does not need to introduce any model considerations regarding the molecular structure of the interfacial layer or utilize particular values of layer thickness. 

Spatial Structures Formed by Chemical Reactions at Liquid Interfaces Phenomenology, Model Simulations, and Pattern Analysis... 

The classic theory due to van der Waals provides an important phenomenological link between the structure of an interface and its interfacial tension [50-52]. The expression... 

The interface between a solid and its vapor (or an inert gas) is discussed in this chapter from an essentially phenomenological point of view. We are interested in surface energies and free energies and in how they may be measured or estimated theoretically. The study of solid surfaces at the molecular level, through the methods of spectroscopy and diffraction, is taken up in Chapter VIII. 

The importance of the solid-liquid interface in a host of applications has led to extensive study over the past 50 years. Certainly, the study of the solid-liquid interface is no easier than that of the solid-gas interface, and all the complexities noted in Section VIM are present. The surface structural and spectroscopic techniques presented in Chapter VIII are not generally applicable to liquids (note, however. Ref. 1). There is, perforce, some retreat to phenomenology, empirical rules, and semiempirical models. The central importance of the Young equation is evident even in its modification to treat surface heterogeneity or roughness. ... 

There is a large volume of contemporary literature dealing with the structure and chemical properties of species adsorbed at the solid-solution interface, making use of various spectroscopic and laser excitation techniques. Much of it is phenomenologically oriented and does not contribute in any clear way to the surface chemistry of the system included are many studies aimed at the eventual achievement of solar energy conversion. What follows here is a summary of a small fraction of this literature, consisting of references which are representative and which also yield some specific information about the adsorbed state. 

The focus of the present chapter is the application of second-order nonlinear optics to probe surfaces and interfaces. In this section, we outline the phenomenological or macroscopic theory of SHG and SFG at the interface of centrosymmetric media. This situation corresponds, as discussed previously, to one in which the relevant nonlinear response is forbidden in the bulk media, but allowed at the interface. 

Figure Bl.5.5 Schematic representation of the phenomenological model for second-order nonlinear optical effects at the interface between two centrosynnnetric media. Input waves at frequencies or and m2, witii corresponding wavevectors /Cj(co and k (o 2), are approaching the interface from medium 1. Nonlinear radiation at frequency co is emitted in directions described by the wavevectors /c Cco ) (reflected in medium 1) and /c2(k>3) (transmitted in medium 2). The linear dielectric constants of media 1, 2 and the interface are denoted by E2, and s, respectively. The figure shows the vz-plane (the plane of incidence) withz increasing from top to bottom and z = 0 defining the interface.

We now consider how one extracts quantitative infonnation about die surface or interface adsorbate coverage from such SHG data. In many circumstances, it is possible to adopt a purely phenomenological approach one calibrates the nonlinear response as a fiinction of surface coverage in a preliminary set of experiments and then makes use of this calibration in subsequent investigations. Such an approach may, for example, be appropriate for studies of adsorption kinetics where the interest lies in die temporal evolution of the surface adsorbate density N. ... 

One can regard the Hamiltonian (B3.6.26) above as a phenomenological expansion in temis of the two invariants Aiand//of the surface. To establish the coimection to the effective interface Hamiltonian (b3.6.16) it is instnictive to consider the limit of an almost flat interface. Then, the local interface position u can be expressed as a single-valued fiinction of the two lateral parameters n(r ). In this Monge representation the interface Hamiltonian can be written as... 

The other class of phenomenological approaches subsumes the random surface theories (Sec. B). These reduce the system to a set of internal surfaces, supposedly filled with amphiphiles, which can be described by an effective interface Hamiltonian. The internal surfaces represent either bilayers or monolayers—bilayers in binary amphiphile—water mixtures, and monolayers in ternary mixtures, where the monolayers are assumed to separate oil domains from water domains. Random surface theories have been formulated on lattices and in the continuum. In the latter case, they are an interesting application of the membrane theories which are studied in many areas of physics, from general statistical field theory to elementary particle physics [26]. Random surface theories for amphiphilic systems have been used to calculate shapes and distributions of vesicles, and phase transitions [27-31]. 

As already mentioned in the Introduction, phenomenological models for amphiphilic systems can be divided into two big classes Ginzburg-Landau models and random interface models. 

These apparent restrictions in size and length of simulation time of the fully quantum-mechanical methods or molecular-dynamics methods with continuous degrees of freedom in real space are the basic reason why the direct simulation of lattice models of the Ising type or of solid-on-solid type is still the most popular technique to simulate crystal growth processes. Consequently, a substantial part of this article will deal with scientific problems on those time and length scales which are simultaneously accessible by the experimental STM methods on one hand and by Monte Carlo lattice simulations on the other hand. Even these methods, however, are too microscopic to incorporate the boundary conditions from the laboratory set-up into the models in a reahstic way. Therefore one uses phenomenological models of the phase-field or sharp-interface type, and finally even finite-element methods, to treat the diffusion transport and hydrodynamic convections which control a reahstic crystal growth process from the melt on an industrial scale. 

Interface slip factor a (m ). This factor is defined as a phenomenological parameter characterizing the lubrication behavior on the phase interface as a slide occurs. 

As demonstrated, Eq. (7) gives complete information on how the weight fraction influences the blend viscosity by taking into account the critical stress ratio A, the viscosity ratio 8, and a parameter K, which involves the influences of the phenomenological interface slip factor a or ao, the interlayer number m, and the d/Ro ratio. It was also assumed in introducing this function that (1) the TLCP phase is well dispersed, fibrillated, aligned, and just forms one interlayer (2) there is no elastic effect (3) there is no phase inversion of any kind (4) A < 1.0 and (5) a steady-state capillary flow under a constant pressure or a constant wall shear stress. 

The division of the interface into an inner layer and a diffuse layer has been a matter of discussion in view of the molecular dimensions of the inner layer.122-126,279-285 However, the contribution of a constant capacitance is an experimental fact. Furthermore, molecular theories for electrolytes near a charged hard wall282 as well as phenomenological nonlocal electrostatic theories283 predict such a component without artificial introduction of any inner layers. This turns out to be an effect of the short-range structure of the solvent.279-285... 

Classical surface and colloid chemistry generally treats systems experimentally in a statistical fashion, with phenomenological theories that are applicable only to building simplified microstructural models. In recent years scientists have learned not only to observe individual atoms or molecules but also to manipulate them with subangstrom precision. The characterization of surfaces and interfaces on nanoscopic and mesoscopic length scales is important both for a basic understanding of colloidal phenomena and for the creation and mastery of a multitude of industrial applications. 

The first controversial point in this mechanism is the nature of the reaction planes where the precursor formation and the ET reaction take place. Samec assumed that the ET step occurs across an ion-free layer composed of oriented solvent molecules [1]. By contrast, Girault and Schiffrin considered a mixed solvent region where electrochemical potentials are dependent on the position of the reactants at the interface [60]. From a general perspective, the phenomenological ET rate constant can be expressed in terms of... 

In our opinion, the interesting photoresponses described by Dvorak et al. were incorrectly interpreted by the spurious definition of the photoinduced charge transfer impedance [157]. Formally, the impedance under illumination is determined by the AC admittance under constant illumination associated with a sinusoidal potential perturbation, i.e., under short-circuit conditions. From a simple phenomenological model, the dynamics of photoinduced charge transfer affect the charge distribution across the interface, thus according to the frequency of potential perturbation, the time constants associated with the various rate constants can be obtained [156,159-163]. It can be concluded from the magnitude of the photoeffects observed in the systems studied by Dvorak et al., that the impedance of the system is mostly determined by the time constant. 

Equation (45) resembles the generalized expression of IMPS for semiconductor-electrolyte interfaces [149,164]. This similarity between the dynamic photoresponses for both types of interfaces is only valid in phenomenological terms, as the natures of the... 

FIG. 21 Complex IMPS spectra obtained for the photo-oxidation of DFcET by ZnYPPC" at the water-DCE interface (a). The opposite potential dependencies of the phenomenological ET rate constant and the porph5rin coverage (b) are responsible for the maximum on the flux of electron injection obtained from IMPS responses for DFcET and Fc (c). The potential dependence of the back electron-transfer rate constant is also shown in (d). (From Ref. 83. Reproduced by permission of The Royal Society of Chemistry.)... 

Nowadays attention is turned also to the supermolecular level, that is, to the morphologic aspects, to the nature of interfaces, to the formation of new phases, or of particular aggregates (liquid crystals, gels, etc.). Interest has also been directed to the study of chain mobility for its influence on frictional properties of polymers. In recent years there have been many successful approaches to a microscopic theory (in contrast to a phenomenological approach) of the physi-comechanical behavior of macromolecular materials. 

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