Schmickler and Henderson

Figure 3.5 The inverse Helmholtz capacity at the pzc as a function of the electronic density the latter is plotted in atomic units (a.u.), where 1 a.u. of density = 6.76 x 1024 cm-3. The dashed line is based on a model calculation of Schmickler and Henderson [3].

A nonprimitive model for the jellium metal-liquid electrolyte interface similar to but more general than that of BRYB was developed by Schmickler and Henderson [132,133]. Their hard sphere ions and solvent molecules had different diameters and the construction of the jellium edge was different. Also their electronic density profile had two adjustable parameters and they assumed that the dependence on metal charge of the nearest distance of approach of solvent molecules to the metal was not important. In one paper [132b] the trial function in Eq. (21) was generalized for x < 0 to read... 

Including fluctuations of the polarization in their calculation, these authors find a weak temperature dependence of the tunnel barrier which confirms the minor dynamical role of the liquid, in agreement with Schmickler and Henderson s assumption [29], The transit time of tunneling electrons estimated by Sebastian and Doyen is 10 s, which is indeed much shorter than the time needed for the solvent molecules to rearrange. Calculations nevertheless show that thermal fluctuations in the polarization can reduce the effective barrier to nearly 1.5 eV, independently of the difference of work functions. 

The first model of electron tunneling through water layers was proposed by W. Schmickler and D. Henderson 1990. "... 

W. Schmickler and D. Henderson, /. Ghent. Phys., 80,3381 (1984). The Interphase Between Jellium and a Hard Sphere Electrolyte. A Model for the Electric Double Layer. 

Schmickler, W., Henderson, D., 1986. The interphase between jeUium and a hard sphere electrol3he capacity—charge characteristics and dipole potentials. J. Chem. Phys. 85, 1650-1657. 

When the two phases separate the distribution of the solvent molecules is inhomogeneous at the interface this gives rise to an additional contribution to the free energy, which Henderson and Schmickler treated in the square gradient approximation [36]. Using simple trial functions, they calculated the density profiles at the interface for a number of system parameters. The results show the same qualitative behavior as those obtained by Monte Carlo simulations for the lattice gas the lower the interfacial tension, the wider is the interfacial region in which the two solvents mix (see Table 3). 

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