Free-electron theory, classical

One further effect of the formation of bands of electron energy in solids is that the effective mass of electrons is dependent on the shape of the E-k curve. If this is the parabolic shape of the classical free electron theory, the effective mass is the same as the mass of the free electron in space, but as this departs from the parabolic shape the effective mass varies, depending on the curvature of the E-k curve. From the definition of E in terms of k, it follows that the mass is related to the second derivative of E with respect to k thus... 

The free-electron theory of metals was developed in three main stages (1) classical free-electron theory, (2) quantum free-electron theory, and (3) band theory. 

Classical Free-Electron Theory, Classical free-electron theory assumes the valence electrons to be virtually free everywhere in the metal. The periodic lattice field of the positively charged ions is evened out into a uniform potential inside the metal. The major assumptions of this model are that (1) an electron can pass from one atom to another, and (2) in the absence of an electric field, electrons move randomly in all directions and their movements obey the laws of classical mechanics and the kinetic theory of gases. In an electric field, electrons drift toward the positive direction of the field, producing an electric current in the metal. The two main successes of classical free-electron theory are that (1) it provides an explanation of the high electronic and thermal conductivities of metals in terms of the ease with which the free electrons could move, and (2) it provides an explanation of the Wiedemann-Franz law, which states that at a given temperature T, the ratio of the electrical (cr) to the thermal (k) conductivities should be the same for all metals, in near agreement with experiment ... 

The Classical Free-Electron Theory. The classical free-electron theory considers that the valence electrons are virtually free everywhere in the metal. The periodic lattice field of the positively charged ions is evened out into a uniform potential inside the metal. The major assumptions of this model are (1) an electron can pass from one atom to another and (2) in the absence of an electric field elec-rons move randomly in all directions, and their movements obey the laws of classical mechanics and the kinetic theory of gases. In an electric field electrons... 

This rule conforms with the principle of equipartition of energy, first enunciated by Maxwell, that the heat capacity of an elementary solid, which reflected the vibrational energy of a three-dimensional solid, should be equal to 3RJK-1 mol-1. The anomaly that the free electron theory of metals described a metal as having a three-dimensional structure of ion-cores with a three-dimensional gas of free electrons required that the electron gas should add another (3/2)R to the heat capacity if the electrons behaved like a normal gas as described in Maxwell s kinetic theory, whereas the quantum theory of free electrons shows that these quantum particles do not contribute to the heat capacity to the classical extent, and only add a very small component to the heat capacity. 

THE MODERN THEORY OFSOLIDS, Frederick Seitz. First inexpensive edition of classic work on theory of ionic crystals, free-electron theory of metals and semiconductors, molecular binding, much more. 736pp. 55 x 814. 

Like many other quasi-classical methods applied within the domain of quantum mechanics, the free electron theory explained the gross features of the phenomenon and provided an attractively simple physical picture. The method did not of course, suggest any parallels with the quantum mechanically based HMO theory (which predicted an alternation in 7c-electron properties among the annulenes). 

The theory of coherent scattering by a classical free electron was developed by J, J, Thompson in 1898. The electron is considered to be a classical free particle of charge - e and of mass m accelerated by the oscillating electric field of the... 

Problems with the Classical Free Electron Gas Theory 18.3.1 Temperature Dependence... 

Another important accomplislnnent of the free electron model concerns tire heat capacity of a metal. At low temperatures, the heat capacity of a metal goes linearly with the temperature and vanishes at absolute zero. This behaviour is in contrast with classical statistical mechanics. According to classical theories, the equipartition theory predicts that a free particle should have a heat capacity of where is the Boltzmann constant. An ideal gas has a heat capacity consistent with tliis value. The electrical conductivity of a metal suggests that the conduction electrons behave like free particles and might also have a heat capacity of 3/fg,... 

An entirely different approach to the correlation problem is taken in the plasma model (Bohm and Pines 1953, Pines 1954, 1955), in which the electrons in a metal are approximated by a free-electron gas moving in a uniform positive background. According to classical discharge theory, such a plasma is characterized by an oscillatory behavior having a frequency... 

So far, only the nuclear reorganization energy attending electron transfer has been discussed, yielding the expressions above of the free energy of activation in the framework of classical transition state theory. A second series of important factors are those that govern the preexponential factor, k, raising in particular the question of the adiabaticity or nonadiabaticity of electron transfer between a molecule and the electronic states in the electrode. 

The Marcus classical free energy of activation is AG , the adiabatic preexponential factor A may be taken from Eyring s Transition State Theory as (kg T /h), and Kel is a dimensionless transmission coefficient (0 < k l < 1) which includes the entire efiFect of electronic interactions between the donor and acceptor, and which becomes crucial at long range. With Kel set to unity the rate expression has only nuclear factors and in particular the inner sphere and outer sphere reorganization energies mentioned in the introduction are dominant parameters controlling AG and hence the rate. It is assumed here that the rate constant may be taken as a unimolecular rate constant, and if needed the associated bimolecular rate constant may be constructed by incorporation of diffusional processes as ... 

The theory fails to explain the molar specific heat of metals since the free electrons do not absorb heat as a gas obeying the classical kinetic gas laws. This problem was solved when Sommerfeld (1) applied quantum mechanics to the electron system. 

Formerly these metallic properties were attributed to the presence of free electrons. The classical theory of this electron gas (Lorentz) leads, however, to absurdities for instance, a specific heat of 3/2 R had to be expected for this monatomic gas, contrary to the experience that Dulong and Petit s rule (atomic specific heat 6/2 R) holds for both conductors and non-conductors. The calculated ratio of heat conductivity to electrical conductivity (Wiedemann-Franz constant) also did not agree with observation. 

Classical density functional theory (DFT) [18,19] treats the cluster formation free energy as a functional of the average density distributions of atoms or molecules. The required input information is an intermolecular potential describing the substances at hand. The boundary between the cluster and the surrounding vapor is not anymore considered sharp, and surface active systems can be studied adequately. DFT discussed here is not to be confused with the quantum mechanical density functional theory (discussed below), where the equivalent of the Schrodinger equation is expressed in terms of the electron density. Classical DFT has been used successfully to uncover why and how CNT fails for surface active systems using simple model molecules [20], but it is not practically applicable to real atmospheric clusters if the molecules are not chain-like, the numerical solution of the problem gets too burdensome, unless the whole molecule is treated in terms of an effective potential. 

By definition, the atomic scattering factor /(x) is given in terms of the amplitude scattered by a single electron at the lattice point. It is useful, however, to have the scattered amplitude/I in terms of the incident amplitude Aq. From classical electromagnetic theory, it follows that if a wave of amplitude Aq is incident on a free electron, the amplitude A of the radiation emitted in the forward direction, at a distance R (meters) from the electron, is given by... 

Classical theories of electrical and thermal conductance assume a huge number of atoms and free electrons. Let s assume a silicon cube with one side dimension of a and with common doping of lO cm. In an n-doped silicon cube with the size of (100 nm) there are 5><10 atoms and 10 free electrons at 300 K, but in the Si cube with the size of (10 nm) there are 5x10 atoms and 1% chance only to find one free electron. Free electrons are necessary for electrical conductance as charge carriers. In order to keep the conductive properties of the semiconductor material one should apply more intensive doping, 10 ° cm. However, such intensive doping decreases resistivity of the material dramatically (from 2x10" Qm to 10 Qm, respectively, for n-type Si, at 300 K). Low number of free electrons should be scattered evenly in whole volume of a material. 

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