Fermi level electron related properties, metals

For electrons in a metal the work function is defined as the minimum work required to take an electron from inside the metal to a place just outside (c.f. the preceding definition of the outer potential). In taking the electron across the metal surface, work is done against the surface dipole potential x So the work function contains a surface term, and it may hence be different for different surfaces of a single crystal. The work function is the negative of the Fermi level, provided the reference point for the latter is chosen just outside the metal surface. If the reference point for the Fermi level is taken to be the vacuum level instead, then Ep = —, since an extra work —eoV> is required to take the electron from the vacuum level to the surface of the metal. The relations of the electrochemical potential to the work function and the Fermi level are important because one may want to relate electrochemical and solid-state properties. 

The band structure and Bloch functions of metals have been extensively published. In particular, the results are compiled as standard tables. The book Calculated Electronic Properties of Metals by Moruzzi, Janak, and Williams (1978) is still a standard source, and a revised edition is to be published soon. Papaconstantopoulos s Handbook of the Band Structure of Elemental Solids (1986) listed the band structure and related information for 53 elements. In Fig. 4.14, the electronic structure of Pt is reproduced from Papaconstantopoulos s book. Near the Fermi level, the DOS of s and p states are much less than 1%. The d states are listed according to their symmetry properties in the cubic lattice (see Kittel, 1963). Type 2 includes atomic orbitals with basis functions xy, yz, xz], and type e, includes 3z - r-), (x - y ). The DOS from d orbitals comprises 98% of the total DOS at the Fermi level. 

The first product formed from water dissociation at positive electrode potentials is surface-bonded hydroxyl OH. Detailed calculations of the properties of chemisorbed OH suggest that it should be viewed upon as a surface hydroxide OH [41], with 8 close to 1. This anionic character is related to the Ire orbital which is occupied by 1 electron in the uncoordinated OH, and whose energy lies below the Fermi level of the metal. Hence electronic charge is transferred from the metal to the OH upon adsorption. The bonding of OH is generally weaker than that of atomic O because of the lower degeneracy of the Ire orbital compared to the 2p orbital on oxygen [41]. 

In order to relate electrochemical behavior to the electronic properties of a metal or of a semiconductor, one must find a relationship between the Fermi level and the reversible potential. In the next paragraph, we develop such a relationship for metals, starting with the half-cell reaction (2.153). 

Here, an is the Bohr orbit radius of the isolated center and nc is the critical carrier density at the M-NM transition. Another way of viewing the transition is that of an electronic instability which ensues when the trapping of an electron into a localized level also removes one electron from the Fermi gas of electrons. This must clearly lead to a further reduction in the screening properties (which are themselves directly related to the conduction electron density) and a catastrophic situation then ensures the localization of electrons from the previously metallic electron gas. 

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