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Let us remark that the respective magnitude of these two effects cannot be extracted from numerical quantum calculations in a simple way: all the surface effects are inter-dependent because the Fermi wavelength, of the order of the spatial radial extent of the low-density electronic surface tail, is much larger than the thickness d of the skin of reduced polarizability.
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0041046244
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1/2. If the above ansatz for describing the dielectric properties of the spillout region is used, the absorption spectrum corresponds to the one of a slightly larger cluster (R′ = R + t) with an inner skin of vanishing ionic-core polarizability of thickness t, and a blue-shift is obtained instead of the expected red-shift. As a matter of fact the model calculations of Fedrigo et al. correspond to those of larger clusters (radius R′ = R + t) involving a skin of reduced polarizability of thickness d′ = d + t = 6.15 a.u. Such a very large value, that is required to fit the experimental data, is due to the fact that the local porosity at the metal/matrix interface is partly responsible for the observed net blue-shift [15] and was not taken into account in reference [12]. This points out that the estimation of the effective thickness d should involve free clusters.
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With regard to embedded clusters, the introduction of an outer vacuum rind for mimicking the local porosity at the metal/matrix interface [15, 16] was however required to bring the model calculations in agreement with experiment.
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0002729557
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43
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85119220086
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note
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c(ω) is then obtained by adding 1 to the curve plotted in the Figure 1 of reference [21].
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47
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