The Electronic Structure of Metal Surfaces

Lang, N. D. (1973). The density-functional formalism and the electronic structure of metal surfaces. In Solid State Physics, edited by H. Ehrenreich, F. Seitz, and D. Turnbull, Vol. 28, Academic, New York. 

RECENT DEVELOPMENTS IN THE ELECTRONIC STRUCTURE OF METAL SURFACES... 

In this communication I will compare the electronic structures of metal surfaces with that of metalloporphyrins and discuss the possibility of isolate non-local electronic perturbations for CO terminally bound to metal surfaces from the vibrational spectra of carbonyl-hemes. 

This section is dedicated to the main focus of the UHV experiments in this thesis, the electronic structure of metal surfaces, supported metal clusters and adsorbate interactions. In the light of the idea to tune reactivity by the modification of the catalyst (i.e. size) a brief introduction of adsorption and the electronic stmcture of the catalyst adsorbate interaction is given Further, an overview over EES results on metal particles and clusters is presented, followed by a sections about EES of adsorbates and the data treatment for comparison to gas phase spectra, applied in this work. 

As we have seen the electronic structure of metal surfaces is likely to differ from that in the bulk. One way, this altered behavior is exemplified is through the formation of so-called surface states [169-172]. The surface states of metals represent interesting physical phenomena in their own right, as examples of confined two-dimensional... 

The failure of the free-electron model to reproduce even pronounced effects in ER is demonstrated in Figure 24. Here, the ER spectra for Cu(lll) on mica are shown for 5- and / -polarization at 45° angle of incidence (solid curves). The pronounced peaks in the experimental spectra at 2.2 eV, at the onset of the interband transition in Cu, cannot be reproduced by the free-electron model alone (dashed curves). A satisfactory agreement between theory and experiment—at least for the spectral shape—was, however, achieved when a shift of the interband transition energy with electrode potential of -0.2 eV/V was included in the calculation. Although the absolute value of this potential-induced band structure change in Cu may be somewhat in question, the result certainly indicates that the electrochemical double layer can influence the electronic structure of metal surfaces. 

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