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Modern Aspects of Electrochemistry, Number 18 by Brian E. Conway, John O'M. Bockris, Ralph E. White

By Brian E. Conway, John O'M. Bockris, Ralph E. White

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Extra info for Modern Aspects of Electrochemistry, Number 18

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Let us first consider the H+ case. In vacuum the ionization potential, Theoretical Aspects of Semiconductor Electrochemistry I I -1- H -L H (a) 25 (b) + Figure 12. (a) Ionization of H to H in vacuum and electron in vacuum at oo. Energy required is the ionization potential, (b) Ionization of H to H + in water and electron in vacuum at oo. Energy required is (/ — W). /, is required to complete the following process (Fig. 12a): H -> H+ + e~ (44) This step is analogous to that of removing an electron from the Fermi level of the solid phase to the vacuum, the energy of which is given by the work function, .

Similar notation is used for the valence band current. N(E), N'(E), W(E), DO(E)9 and DR(E) represent the number of occupied and unoccupied states in the semiconductor, tunneling probability, and the distribution of occupied (reduced) and of unoccupied (oxidized) state of redox couple, respectively, between energy E and E + dE. E is taken as zero at the bottom of the valence band, cR and c% are the surface concentrations of reduced and oxidized species, respectively. In Sections II and III we correlated the electronic energy level of the solid phase, EF, and that of electrolyte, Vredox.

13, only the states at which the H+-H2O distance is larger than/ are allowed and in Fig. 14, only the states at which the Cr~H 2 O distance is larger than m are allowed. It seems, however, that there is no reason to inhibit the states in which the ion-water distance is shorter than its ground level. Thus, there should be energy levels with E < Eo for a positive ion and with E > Eo for a negative ion. Equation (50) should be used if E > Eo and Eq. (51) should be used if E < Eo. The value of y depends on the shape of the potential energy curve of an ion before and after neutralization.

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