Arbitrary Potential Case

For simplicity, we consider the case where two parallel plates 1 and 2 at separation h are immersed in a symmetrical electrolyte solution of valence z and bulk concentration n. 

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For the arbitrary potential case, we use the relationship between the surface charge density a and the surface potential i/ o derived in Chapter 1. In the following, we consider the cases of a plate-like particle, a spherical particle, and a cylindrical particle [3],... 

In the frame of the present review, we discussed different approaches for description of an overdamped Brownian motion based on the notion of integral relaxation time. As we have demonstrated, these approaches allow one to analytically derive exact time characteristics of one-dimensional Brownian diffusion for the case of time constant drift and diffusion coefficients in arbitrary potentials and for arbitrary noise intensity. The advantage of the use of integral relaxation times is that on one hand they may be calculated for a wide variety of desirable characteristics, such as transition probabilities, correlation functions, and different averages, and, on the other hand, they are naturally accessible from experiments. 

In this chapter, we discuss two models for the electrostatic interaction between two parallel dissimilar hard plates, that is, the constant surface charge density model and the surface potential model. We start with the low potential case and then we treat with the case of arbitrary potential. 

We first define the rest interaction V for the case that the one-particle spectrum has obtained by means of an arbitrary potential V. In the Goldstone program, this operator can be assigned to the variable Vrest by entering... 

In the literature, a large number of various formulae for the electrostatic interaction energies can be found, derived under various approximations. Ohshima (33) has derived an equation for the interaction energy between two spherical particles in the low-potential case. However, the resulting equation is rather complicated. Efforts have been made to derive simple but yet accurate analytical equations for the interaction energy. In this respect, substantial progress has been made by Camie and co-workers (36, 37). For spherical particles at an arbitrary surface potential, relatively simple equations have been derived. The approximations in the Pois-son-Boltzmann equation are, of course, still included. 

The quantum degrees of freedom are described by a wave function /) = (x, t). It obeys Schrodinger s equation with a parameterized coupling potential V which depends on the location q = q[t) of the classical particles. This location q t) is the solution of a classical Hamiltonian equation of motion in which the time-dependent potential arises from the expectation value of V with regard to tp. For simplicity of notation, we herein restrict the discussion to the case of only two interacting particles. Nevertheless, all the following considerations can be extended to arbitrary many particles or degrees of freedom. 

In the case of ions in solution, and of gases, the chemical potential will depend upon concentration and pressure, respectively. For ions in solution the standard chemical potential of the hydrogen ion, at the temperature and pressure under consideration, is given an arbitrary value of zero at a specified concentration... 

Electrochemical reactions differ fundamentally from chemical reactions in that the kinetic parameters are not constant (i.e., they are not rate constants ) but depend on the electrode potential. In the typical case this dependence is described by Eq. (6.33). This dependence has an important consequence At given arbitrary values of the concentrations d c, an equilibrium potential Eq exists in the case of electrochemical reactions which is the potential at which substances A and D are in equilibrium with each other. At this point (Eq) the intermediate B is in common equilibrium with substances A and D. For this equilibrium concentration we obtain from Eqs. (13.9) and (13.11),... 

We shall not discuss all the numerous energy minimisation procedures which have been worked out and described in the literature but choose only the two most important techniques for detailed discussion the steepest descent process and the Newton-Raphson procedure. A combination of these two techniques gives satisfactory results in almost all cases of practical interest. Other procedures are described elsewhere (1, 2). For energy minimisation the use of Cartesian atomic coordinates is more favourable than that of internal coordinates, since for an arbitrary molecule it is much more convenient to derive all independent and dependent internal coordinates (on which the potential energy depends) from an easily obtainable set of independent Cartesian coordinates, than to evaluate the dependent internal coordinates from a set of independent ones. Furthermore for our purposes the use of Cartesian coordinates is also advantageous for the calculation of vibrational frequencies (Section 3.3.). The disadvantage, that the potential energy is related to Cartesian coordinates in a more complex fashion than to internals, is less serious. 

Finally we note that the presented approaches may be easily generalized for the case of multidimensional systems with axial symmetry. The generalization for arbitrary multidimensional potentials had been discussed in Refs. 41 and 114. 

Let us prove that formula (4.19) (in this particular case for c = — oo) not only gives values of moments of FPT of the absorbing boundary, but also expresses moments of transition time of the system with noise, described by an arbitrary symmetric with respect to the point d potential profile. 

Before finding the Laplace-transformed probability density wj(s, zo) of FPT for the potential, depicted in Fig. A 1(b), let us obtain the Laplace-transformed probability density wx s, zo) of transition time for the system whose potential is depicted in Fig. Al(c). This potential is transformed from the original profile [Fig. Al(a)] by the vertical shift of the right-hand part of the profile by step p which is arbitrary in value and sign. So far as in this case the derivative dpoints except z = 0, we can use again linear-independent solutions U(z) and V(z), and the potential jump that equals p at the point z = 0 may be taken into account by the new joint condition at z = 0. The probability current at this point is continuous as before, but the probability density W(z, t) has now the step, so the second condition of (9.4) is the same, but instead of the first one we should write Y (0) + v1 (0) = YiiOje f1. It gives new values of arbitrary constants C and C2 and a new value of the probability current at the point z = 0. Now the Laplace transformation of the probability current is... 

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