Periodic surfaces computational method

The three-dimensional symmetry is broken at the surface, but if one describes the system by a slab of 3-5 layers of atoms separated by 3-5 layers of vacuum, the periodicity has been reestablished. Adsorbed species are placed in the unit cell, which can exist of 3x3 or 4x4 metal atoms. The entire construction is repeated in three dimensions. By this trick one can again use the computational methods of solid-state physics. The slab must be thick enough that the energies calculated converge and the vertical distance between the slabs must be large enough to prevent interaction. 

In what follows we will discuss systems with internal surfaces, ordered surfaces, topological transformations, and dynamical scaling. In Section II we shall show specific examples of mesoscopic systems with special attention devoted to the surfaces in the system—that is, periodic surfaces in surfactant systems, periodic surfaces in diblock copolymers, bicontinuous disordered interfaces in spinodally decomposing blends, ordered charge density wave patterns in electron liquids, and dissipative structures in reaction-diffusion systems. In Section III we will present the detailed theory of morphological measures the Euler characteristic, the Gaussian and mean curvatures, and so on. In fact, Sections II and III can be read independently because Section II shows specific models while Section III is devoted to the numerical and analytical computations of the surface characteristics. In a sense, Section III is robust that is, the methods presented in Section III apply to a variety of systems, not only the systems shown as examples in Section II. Brief conclusions are presented in Section IV. 

In this section, we introduce the computational method in the form used for the surfaces exhibited in Section IV, i.e., where the prescribed mean curvature of the computed surface is everywhere constant and the boundary conditions are determined by two dual periodic graphs. We also give generalizations of the method for the computation for a surface of prescribed—not necessarily constant—mean curvature, with prescribed contact angle against surface. Generalization to the computation of space curves of prescribed curvature or geodesic curvature is available (Anderson 1986). 

Nevertheless, in spite of the development of computer systems (hardware and software.) it remains a difficult task to deal with heterogeneous catalysis. To computationally model the surface of the heterogeneous catalysts, two big branches have been developed a) the periodic and b) the local methods. The periodic methods use the periodic symmetry of the solid to simulate extended surfaces. These methods allow a proper material representation and reasonable calculations of physical properties such as the Fermi levels. However, they do not seem to properly describe the electronic correlation and, additionally, they present problems with the excited states. Moreover, in order to model the defects of the solid such as comers, etc, where, in general, the active sites of a catalyst arc located, the periodic methods need to use large unitary cells diminishing the advantage of the utilization of the periodic symmetry. 

Another special case of weak heterogeneity is found in the systems with stepped surfaces [97,142-145], shown schematically in Fig. 3. Assuming that each terrace has the lattice structure of the exposed crystal plane, the potential field experienced by the adsorbate atom changes periodically across the terrace but exhibits nonuniformities close to the terrace edges [146,147]. Thus, we have here another example of geometrically induced energetical heterogeneity. Adsorption on stepped surfaces has been studied experimentally [95,97,148] as well as with the help of both Monte Carlo [92-94,98,99,149-152] and molecular dynamics [153,154] computer simulation methods. 

Density functional theory (DFT),32 also a semi-empirical method, is capable of handling medium-sized systems of biological interest, and it is not limited to the second row of the periodic table. DFT has been used in the study of some small protein and peptide surfaces. Nevertheless, it is still limited by computer speed and memory. DFT offers a quantum mechanically based approach from a fundamentally different perspective, using electron density with an accuracy equivalent to post Hartree-Fock theory. The ideas have been around for many years,33 34 but only in the last ten years have numerous studies been published. DFT, compared to ab initio... 

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