Surface-induced liquid structure

The second type, of more importance, is a force due to surface-induced liquid structure. At a conceptual level we have already encountered such a force in the double-layer. There the electrolyte can be regarded as the liquid , with the suspending water a continuum backgroimd that affects the problem only through its dielectric constant. The bulk liquid electrolyte has a uniform distribution of cations and anions. In the presence of the charged surface, that uniform distribution changes. The overlap in profile of the surface induced liquid structure causes the force. 

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Forces due to overlap of profiles of surface induced liquid structure... 

The interaction of complex liquid crystal molecules with realistic surfaces is an area which is currently unexplored using electronic structure methods though, as stated earlier, the problem of surface-induced control of molecular orientation remains at the forefront of liquid crystal device technology. This problem is currently at the limits of practical capability of the most powerful computer systems. However treatment of a single mesogenic molecule on a... 

The importance of surface characterization in molecular architecture chemistry and engineering is obvious. Solid surfaces are becoming essential building blocks for constructing molecular architectures, as demonstrated in self-assembled monolayer formation [6] and alternate layer-by-layer adsorption [7]. Surface-induced structuring of liqnids is also well-known [8,9], which has implications for micro- and nano-technologies (i.e., liqnid crystal displays and micromachines). The virtue of the force measurement has been demonstrated, for example, in our report on novel molecular architectures (alcohol clusters) at solid-liquid interfaces [10]. 

Other forces can arise as a result of elastic strain on the growing film, which can be due to a surface-induced ordering in the first few layers that reverts to the bulk liquid structure at larger distances. This elastic energy is stored in intermolecular distances and orientations that are stretched or compressed from the bulk values by the influence of the substrate at short distances [7]. Similar phenomena are well known to occur in the growth of epitaxial layers in metals and semiconductors. 

Complementing the equilibrium measurements will be a series of time resolved studies. Dynamics experiments will measure solvent relaxation rates around chromophores adsorbed to different solid-liquid interfaces. Interfacial solvation dynamics will be compared to their bulk solution limits, and efforts to correlate the polar order found at liquid surfaces with interfacial mobility will be made. Experiments will test existing theories about surface solvation at hydrophobic and hydrophilic boundaries as well as recent models of dielectric friction at interfaces. Of particular interest is whether or not strong dipole-dipole forces at surfaces induce solid-like structure in an adjacent solvent. If so, then these interactions will have profound effects on interpretations of interfacial surface chemistry and relaxation. 

Chu X L, Nikolov AD, Wasan DT (1995) Thin liquid film structime and stability The role of depletion and surface-induced structural forces. J Chem Phys 103 6653-6661... 

W. Norde and T. Zoungrana, Surface-induced changes in the structure and activity of enzymes physically immobilized at solid/liquid interfaces, Biotechnol. Appl. Biochem. 28, 133-143 (1998). 

The sensitivity of deuteron NMR to the molecular orientational order and to director field configurations turned out to be extremely useful in studies of liquid crystals confined into snbmicrometer pores. Moreover, the large surface-to-volume ratio of these composite systems render the interfacial and surface phenomena, induced by the liquid crystal-surface interactions, accessible even to an essentially integrative technique like NMR. Since the discovery of polymer dispersed liquid crystals (PDLCs) in 1986 [4], NMR of selectively deuterated liquid crystals was used to discriminate unambiguously among various director structures in cavities, resulting from an interplay between elastic forces, morphology and size of the cavity, and surface interactions. These structures include the escaped-radial, planar axial, planar-polar, and... 

The surface-induced layering of molecules has some interesting consequences, when a liquid is confined between two flat surfaces, and the separation between the surfaces is reduced to molecular dimensions. When the surface separation is changed, an oscillatory force is detected on both surfaces, which is due to layering of molecules near both walls. This can be intuitively understood as a result of periodic match or mismatch between the number of molecular layers and the total surface separation D. As this force originates from the local structure of a liquid, it is usually called the structural (or solvation) force [2]. 

The state of polarization of light, reflected from an interface, depends strongly on the profile of the dielectric constant across that interface. This simple principle is used in the Brewster angle reflection ellipsometry (BAE), where one measures the ellipticity coefficient of light, reflected from an interface. The method is sensitive enough to detect extremely small changes in the structure of liquid crystalline-solid interfaces. Subnanometer resolution of the adsorption parameter is routinely achieved. The method is therefore very useful for the study of liquid crystal interfaces, where the surface-induced variation of the order can be observed [5,25,33-41]. 

The application of the previously discussed techniques to induce monodomain structures in side-chain liquid-crystalline polymers by the application of electric or electromagnetic fields, by shearing or on anisotropic surfaces, frequently leads to comparatively low, macroscopically uniform orientation. Additionally, the methods are limited to a sample thickness of about 100 pm. Liquid-crystalline side-chain elastomers do not have this restriction, because a high macroscopic orientation can be induced in polymeric networks by mechanical deformation up to a sample thickness of about a centimeter [103, 109]. The synthesis of such systems can be performed by crosslinking linear, side-chain liquid-crystalline polymers to networks [llOj. The inherent combination of rubber elasticity and liquid-crystalline phase behavior, may then be exploited for the induction of a macroscopic mesogen orientation by mechanical deformation. 

In the oblique evaporation process, a micro columnar structure is realized on the substrate surface, due to the self shadowing effect as shown in Fig. 3.3.1. When a nematic liquid crystal contacts such a surface, elastic deformation of the liquid crystal along the surface induces an interaction energy between the surface and the nematic material. This is thought to be the driving force for alignment of the nematic director. 

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