Point force approximation technique

In the point force approximation technique (see Section Ic), Burgers (BIO) suggested a polynomial approximation for the distributed line force along the axis of a body of large aspect ratio ... 

When the gap width between two particles becomes very small, numerical calculations involved in both the bispherical coordinate method and the boundary collocation technique are computationally intensive because the number of terms in the series required to be retained to achieve a desired accuracy increases tremendously. To solve this near-contact motion more effectively and accurately, Loewenberg and Davis [43] developed a lubrication solution for the electrophoretic motion of two spherical particles in near contact along their line of centers with the assumption of infinitely thin ion cloud. The axisymmetric motion of the two particles in near contact can be approximated as the pairwise motion of the spheres in point contact plus a deviation stemming from their relative motion caused by the contact force. The lubrication results agree very well with those obtained from the collocation method. It is shown that near contact electrophoretic interparticle... 

It was soon realised that at least unequal intervals, crowded closely around the UMDE edge, might help with accuracy, and Heinze was the first to use these in 1986 [300], as well as Bard and coworkers [71] in the same year. Taylor followed in 1990 [545]. Real Crank-Nicolson was used in 1996 [138], in a brute force manner, meaning that the linear system was simply solved by LU decomposition, ignoring the sparse nature of the system. More on this below. The ultimate unequal intervals technique is adaptive FEM, and this too has been tried, beginning with Nann [407] and Nann and Heinze [408,409], and followed more recently by a series of papers by Harriman et al. [287,288,289, 290,291,292,293], some of which studies concern microband electrodes and recessed UMDEs. One might think that FEM would make possible the use of very few sample points in the simulation space however, as an example, Harriman et al. [292] used up to about 2000 nodes in their work. This is similar to the number of points one needs to use with conformal mapping and multi-point approximations in finite difference methods, for similar accuracy. 

Rigorous formulations of the problems associated with solvation necessitate approximations. From the computational point of view, we are forced to consider interactions between a solute and a large number of solvent molecules which requires approximate models [75]. The microscopic representation of solvent constitutes a discrete model consisting of the solute surrounded by individual solvent molecules, generally only those in close proximity. The continuous model considers all the molecules surrounding the solvent but not in a discrete representation. The solvent is represented by a polarizable dielectric continuous medium characterized by macroscopic properties. These approximations, and the use of potentials, which must be estimated with empirical or approximate computational techniques, allows for calculations of the interaction energy [75],... 

Until this point, the consideration of electron-electron repulsion terms has been neglected in the molecular Hamiltonian. Of course, an accurate molecular Hamiltonian must account for these forces, even though an explicit term of this type renders exact solution of the Schrddinger equation impossible. The way around this obstacle is the same Hartree-Fock technique that is used for the solution of the Schrddinger equation in many-electron atoms. A Hamiltonian is constructed in which an effective potential of the other electrons substitutes for a true electron-electron reg sion term. The new operator is called the Lock operator, F. The orbital approximation is still used so that F can be separated into i (the total number of electrons) one-electron operators, Fi (19). 

Next, the forces need to be calculated that have an effect on the atoms of the reacting system. To this end, the first derivatives of the potential energy with respect to coordinates should have to be calculated in a great number of points and the values obtained approximated by analytical expressions. However, so as to reduce calculation work, a different technique is commonly applied the forces along a trajectory are calculated from the quantum mechanical expressions for the potential surface [100, 101]. This procedure takes about 80% of the total calculation time, the rest is spent on integrating the equations of motion. 

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