Electrons in metals

In this chapter, the foundations of equilibrium statistical mechanics are introduced and applied to ideal and weakly interacting systems. The coimection between statistical mechanics and thennodynamics is made by introducing ensemble methods. The role of mechanics, both quantum and classical, is described. In particular, the concept and use of the density of states is utilized. Applications are made to ideal quantum and classical gases, ideal gas of diatomic molecules, photons and the black body radiation, phonons in a hannonic solid, conduction electrons in metals and the Bose—Einstein condensation. Introductory aspects of the density... 

For insulators, Z is very small because p is very high, ie, there is Htde electrical conduction for metals, Z is very small because S is very low. Z peaks for semiconductors at - 10 cm charge carrier concentration, which is about three orders of magnitude less than for free electrons in metals. Thus for electrical power production or heat pump operation the optimum materials are heavily doped semiconductors. 

As might be anticipated, tire above relationship does not imply that electrons in metals are essentially different in mass from the elecU on in free space, but merely that the response of these electrons to an applied force is different, being reflected in the effective mass. 

As described above, quantum restrictions limit tire contribution of tire free electrons in metals to the heat capacity to a vety small effect. These same electrons dominate the thermal conduction of metals acting as efficient energy transfer media in metallic materials. The contribution of free electrons to thermal transport is very closely related to their role in the transport of electric current tlrrough a metal, and this major effect is described through the Wiedemann-Franz ratio which, in the Lorenz modification, states that... 

ESR can detect unpaired electrons. Therefore, the measurement has been often used for the studies of radicals. It is also useful to study metallic or semiconducting materials since unpaired electrons play an important role in electric conduction. The information from ESR measurements is the spin susceptibility, the spin relaxation time and other electronic states of a sample. It has been well known that the spin susceptibility of the conduction electrons in metallic or semimetallic samples does not depend on temperature (so called Pauli susceptibility), while that of the localised electrons is dependent on temperature as described by Curie law. 

In order to give you some background to Slater s Xa method, I would like to describe some very simple models that were used many years ago in order to understand the behaviour of electrons in metallic conductors. 

The Mechanism of Electrical Conduction. Let us first give some description of electrical conduction in terms of this random motion that must exist in the absence of an electric field. Since in electrolytic conduction the drift of ions of either sign is quite similar to the drift of electrons in metallic conduction, we may first briefly discuss the latter, where we have to deal with only one species of moving particle. Consider, for example, a metallic bar whose cross section is 1 cm2, and along which a small steady uniform electric current is flowing, because of the presence of a weak electric field along the axis of the bar. Let the bar be vertical and in Fig. 16 let AB represent any plane perpendicular to the axis of the bar, that is to say, perpendicular to the direction of the cuirent. 

What is the nature of the metallic bond This bond, like all others, forms because the electrons can move in such a way that they are simultaneously near two or more positive nuclei. Our problem is to obtain some insight into the special way in which electrons in metals do this. 

We have seen that the reasons for the mobility of electrons in metals are that they are readily removed from the atom (the ionization energy is... 

Wigner, E., Trans. Faraday Soc. 34, 678, "Effects of the electron interaction on the energy levels of electrons in metals."... 

Plaskett, J. S., Phil. Mag. 45, 1255, "Self-trapped electrons in metals."... 

The common example of real potential is the electronic work ftmction of the condensed phase, which is a negative value of af. This term, which is usually used for electrons in metals and semiconductors, is defined as the work of electron transfer from the condensed phase x to a point in a vacuum in close proximity to the surface of the phase, hut heyond the action range of purely surface forces, including image interactions. This point just outside of the phase is about 1 pm in a vacuum. In other dielectric media, it is nearer to the phase by e times, where e is the dielectric constant. 

The electrochemical potential of single ionic species cannot be determined. In systems with charged components, all energy effects and all thermodynamic properties are associated not with ions of a single type but with combinations of different ions. Hence, the electrochemical potential of an individual ionic species is an experimentally undefined parameter, in contrast to the chemical potential of uncharged species. From the experimental data, only the combined values for electroneutral ensembles of ions can be found. Equally inaccessible to measurements is the electrochemical potential, of free electrons in metals, whereas the chemical potential, p, of the electrons coincides with the Fermi energy and can be calculated very approximately. 

At the contact of two electronic conductors (metals or semiconductors— see Fig. 3.3), equilibrium is attained when the Fermi levels (and thus the electrochemical potentials of the electrons) are identical in both phases. The chemical potentials of electrons in metals and semiconductors are constant, as the number of electrons is practically constant (the charge of the phase is the result of a negligible excess of electrons or holes, which is incomparably smaller than the total number of electrons present in the phase). The values of chemical potentials of electrons in various substances are of course different and thus the Galvani potential differences between various metals and semiconductors in contact are non-zero, which follows from Eq. (3.1.6). According to Eq. (3.1.2) the electrochemical potential of an electron in... 

Magnets producing fields more than 50 T are used to apply quantizing fields for experiments on electrons in metals and in semiconductors. 

In the case of (3) there are, on each metal atom, six electrons not required for Fe=Fe, Fe-acetylene or Fe-CO a bonding. This situation contrasts sharply with that in, for example,an Mo2Xe1+ species, where there are no electrons in metal orbitals other than those in the Mo=Mo bond and the Mo-X a bonds. 

The behaviour of electrons in metals shows the translational properties of quantum particles having quantized energy levels. These cannot be approximated to the continuous distribution describing particles in a gas because of the much smaller mass of the electron when compared with atoms. If one gram-atom of a metal is contained in a cube of length L, the valence electrons have quantum wavelengths, X, described by the de Broglie equation... 

J. H. Alonso and N. H. March, Electrons in Metals and Alloys. London Academic Press, 1989. 

The free movement of electrons in metals makes it easy for metals to be shaped and drawn into wires. 

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