Resting potential, theory

Wagner-Traud Diagram, According to the mixed-potential theory, the overall reaction of the electroless deposition, [Eq. (8.2)] can be described electrochemically in terms of three current-potential i-E) curves, as shown schematically in Eigure 8.2. First, there are two current-potential curves for the partial reactions (solid curves) (1) ic =f(E), the current-potential curve for the reduction of ions, recorded from the rest potential E eq M the absence of the reducing agent Red (when the activity of is equal to 1, eq,M E m) and (2) = f(E), the current-potential... 

Until this point, we have avoided details about the nature of the current flow and mechanisms causing the action potential. This is because certain mechanisms are generally accepted as explanations for the action potential, but, related to establishment of the cell resting potential (see box. Section 3.8), there are alternative theories. 

An Improved Theory of Cellular Resting Potential Incorporating Cooperative Interaction among Surface Anionic Sites... 

Various theories have been proposed to explain the nature of the irreversible rest potential. Perhaps the oldest one is the oxide theory,which considers the rest potential as corresponding to the equilibrium potential of the metal-metal oxide reaction. This, however, contradicts point (3) above, as well as the fact that this rest potential is established also on electrodes free of bulk oxides such as gold and prereduced Pt. Other theories involve the concept of a mixed potential, which is the result of simultaneous occurrence of two or more continuous (steady state) electrode reactions, i.e., the four-electron cathodic reduction of O2 plus some anodic reaction. The result is a zero overall current and a rest potential in between the equilibrium potentials of these reactions. 

Measurement of the rest potential of a corrosion-resistant barrier coating on an active substrate provides a rapid and essential nondestructive means of assessing coating integrity. Mixed potential theory predicts that the corrosion potential... 

We close these introductory remarks with a few comments on the methods which are actually used to study these models. They will for the most part be mentioned only very briefly. In the rest of this chapter, we shall focus mainly on computer simulations. Even those will not be explained in detail, for the simple reason that the models are too different and the simulation methods too many. Rather, we refer the reader to the available textbooks on simulation methods, e.g.. Ref. 32-35, and discuss only a few technical aspects here. In the case of atomistically realistic models, simulations are indeed the only possible way to approach these systems. Idealized microscopic models have usually been explored extensively by mean field methods. Even those can become quite involved for complex models, especially for chain models. One particularly popular and successful method to deal with chain molecules has been the self-consistent field theory. In a nutshell, it treats chains as random walks in a position-dependent chemical potential, which depends in turn on the conformational distributions of the chains in... 

Molecular mechanics force fields rest on four fundamental principles. The first principle is derived from the Bom-Oppenheimer approximation. Electrons have much lower mass than nuclei and move at much greater velocity. The velocity is sufficiently different that the nuclei can be considered stationary on a relative scale. In effect, the electronic and nuclear motions are uncoupled, and they can be treated separately. Unlike quantum mechanics, which is involved in determining the probability of electron distribution, molecular mechanics focuses instead on the location of the nuclei. Based on both theory and experiment, a set of equations are used to account for the electronic-nuclear attraction, nuclear-nuclear repulsion, and covalent bonding. Electrons are not directly taken into account, but they are considered indirectly or implicitly through the use of potential energy equations. This approach creates a mathematical model of molecular structures which is intuitively clear and readily available for fast computations. The set of equations and constants is defined as the force... 

According to RG theory [11, 19, 20], universality rests on the spatial dimensionality D of the systems, the dimensionality n of the order parameter (here n = 1), and the short-range nature of the interaction potential 0(r). In D = 3, short-range means that 0(r) decays as r p with p>D + 2 — tj = 4.97 [21], where rj = 0.033 is the exponent of the correlation function g(r) of the critical fluctuations [22] (cf. Table I). Then, the critical exponents map onto those of the Ising spin-1/2 model, which are known from RG calculations [23], series expansions [11, 12, 24] and simulations [25, 26]. For insulating fluids with a leading term of liquid metals [27-29] the experimental verification of Ising-like criticality is unquestionable. 

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