Free-electron region

Photoemission has been proved to be a tool for measurement of the electronic structure of metal nanoparticles. The information is gained for DOS in the valence-band region, ionization threshold, core-level positions, and adsorbate structure. In a very simplified picture photoemission transforms the energy distribution of the bounded electrons into the kinetic energy distribution of free electrons leaving the sample, which can easily be measured ... 

Thus, the free-electron model is not valid when Eq. (3.7) applies since the wave is reflected. The E,k) curve constructed on this basis is like that obtained from the Kronig-Penney model bands of allowed and forbidden energy regions. 

In conclusion we stress once more that the above-considered mechanism of the effect of illumination on the adsorptivity and catalytic activity of a semiconductor holds in the case when the absorption of light increases the number of free electrons or holes (or both) in the crystal. This, however, does not always take place. The absorption of light by the crystal may proceed by an exciton mechanism. This seems to be the case in the region of intrinsic absorption, which is as a rule photoelectrically inactive. 

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