Charged surface, free energy

While in previous ab initio smdies the reconstructed surface was mostly simulated as Au(lll), Feng et al. [2005] have recently performed periodic density functional theory (DFT) calculations on a realistic system in which they used a (5 x 1) unit cell and added an additional atom to the first surface layer. In their calculations, the electrode potential was included by charging the slab and placing a reference electrode (with the counter charge) in the middle of the vacuum region. From the surface free energy curves, which were evaluated on the basis of experimentally measured capacities, they concluded that there is no necessity for specific ion adsorption [Bohnen and Kolb, 1998] and that the positive surface charge alone would be sufficient to lift the reconstmction. 

One of the most obvious properties of a disperse system is the vast interfacial area that exists between the dispersed phase and the dispersion medium [48-50]. When considering the surface and interfacial properties of the dispersed particles, two factors must be taken into account the first relates to an increase in the surface free energy as the particle size is reduced and the specific surface increased the second deals with the presence of an electrical charge on the particle surface. This section covers the basic theoretical concepts related to interfacial phenomena and the characteristics of colloids that are fundamental to an understanding of the behavior of any disperse systems having larger dispersed phases. 

It is found that for metals, low temperature field evaporation almost always produces surfaces with the (1 x 1) structure, or the structure corresponding to the truncation of a solid. A few such surfaces have already been shown in Fig. 2.32. That this should be so can be easily understood. For metals, field penetration depth is usually less than 0.5 A,1 or much smaller than both the atomic size and the step height of the closely packed planes. Low temperature field evaporation proceeds from plane edges of these closely packed planes where the step height is largest and atoms are also much more exposed to the applied field. Atoms in the middle of the planes are well shielded from the applied field by the itinerant electronic charges which will form a smooth surface to lower the surface free energy, and these atoms will not be field evaporated. Therefore the surfaces produced by low temperature field evaporation should have the same structures as the bulk, or the (lxl) structures, and indeed with a few exceptions most of the surfaces produced by low temperature field evaporation exhibit the (1 x 1) structures. 

The same results (eqs 12a,b and 31) were obtained using a variational method. The details are given in Appendix. At constant surface charge, the free energy is given by... 

The Use of Positively Charged or Low Surface Free Energy Coatings versus Polymer Brushes in Controlling Biofilm Formation... 

The surface free energy, Fs, of the protein can be calculated in terms of two parameters A, the area of the molecule in contact with the solution, and a, the surface charge density (a = charge per A) ... 

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