Quantum free-electron theory

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. 

Quantum Free-Electron Theory Constant-Potential Model, The simple quantum free-electron theory (1) is based on the electron-in-a-box model, where the box is the size of the crystal. This model assumes that (1) the positively charged ions and all other electrons (nonvalence electrons) are smeared out to give a constant background potential (a potential box having a constant interior potential), and (2) the electron cannot escape from the box boundary conditions are such that the wavefunction if/ is... 

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. 

Lorentz1 advanced a theory of metals that accounts in a qualitative way for some of their characteristic properties and that has been extensively developed in recent years by the application of quantum mechanics. He thought of a metal as a crystalline arrangement of hard spheres (the metal cations), with free electrons moving in the interstices.. This free-electron theory provides a simple explanation of metallic luster and other optical properties, of high thermal and electric conductivity, of high values of heat capacity and entropy, and of certain other properties. 

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). 

Sharp drops after certain sizes in the abundance spectrum indicate enhanced stability of these clusters compared to neighboring sizes. We will try to understand this phenomenon from the behavior of valence electrons in the clusters by invoking simple quantum mechanical models. The simplest model one uses for valence electrons inside a bulk metal is the free-electron theory valence electrons of all the atoms are free to move over the entire volume occupied by the solid [11]. One can use a similar free electron model in case of metal clusters. As the simplest approximation, shape of the cluster can be taken as spherical, and the electrons strictly confined within the sphere. In this hard sphere model, the Schrbdinger equation describing the valence electrons is... 

Figure 11. The solid line depicts the quantum adiabatic free energy curve for the Fe /Fe electron transfer at the water/Pt(lll) interface (obtained by using the Anderson-Newns model, path integral quantum transition state theory, and the umbrella sampling of molecular dynamics. The dashed line shows the curve from the classical calculation as given in Fig. 5. (Reprinted from Ref 14.)...

The free-electron model is a simplified representation of metallic bonding. While it is helpful for visualizing metals at the atomic level, this model cannot sufficiently explain the properties of all metals. Quantum mechanics offers a more comprehensive model for metallic bonding. Go to the web site above, and click on Web Links. This will launch you into the world of molecular orbitals and band theory. Use a graphic organizer or write a brief report that compares the free-electron and band-theory models of metallic bonding. 

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. 

The general Jacobian problem associated with the transformation of a density Pi(r) into a density p2(r) (where these densities differ from that of the free-electron gas) was discussed by Moser in 1965 [58]. This work was not performed in the framework of orbital transformations - which might have interested chemists, nor was it done in the context of density functional theory - which might have attracted the attention of physicists. It was a paper written for mathematicians and, as such, it remained unknown to the quantum chemistry community. In the discussion that follows, we use the more accessible reformulation of Bokanowski and Grebert (1995) [65] which relies heavily on the work of Zumbach and Maschke (1983) [61]. Let us define as ifjy = the space of... 

Sommerfeld modified the Drude theory by introducing the laws of quantum mechanics. According to quantum mechanics, electrons are associated with a wave character, the wavelength A being given by A = /i/p where p is the momentum, mv. It is convenient to introduce a parameter, k, called the wave vector, to specify free electrons in metals the magnitude of the wave vector is given by... 

Models for the electronic structure of polynuclear systems were also developed. Except for metals, where a free electron model of the valence electrons was used, all methods were based on a description of the electronic structure in terms of atomic orbitals. Direct numerical solutions of the Hartree-Fock equations were not feasible and the Thomas-Fermi density model gave ridiculous results. Instead, two different models were introduced. The valence bond formulation (5) followed closely the concepts of chemical bonds between atoms which predated quantum theory (and even the discovery of the electron). In this formulation certain reasonable "configurations" were constructed by drawing bonds between unpaired electrons on different atoms. A mathematical function formed from a sum of products of atomic orbitals was used to represent each configuration. The energy and electronic structure was then... 

One of the most important theoretical contributions of the 1970s was the work of Rudnick and Stern [26] which considered the microscopic sources of second harmonic production at metal surfaces and predicted sensitivity to surface effects. This work was a significant departure from previous theories which only considered quadrupole-type contributions from the rapid variation of the normal component of the electric field at the surface. Rudnick and Stern found that currents produced from the breaking of the inversion symmetry at the cubic metal surface were of equal magnitude and must be considered. Using a free electron model, they calculated the surface and bulk currents for second harmonic generation and introduced two phenomenological parameters, a and b , to describe the effects of the surface details on the perpendicular and parallel surface nonlinear currents. In related theoretical work, Bower [27] extended the early quantum mechanical calculation of Jha [23] to include interband transitions near their resonances as well as the effects of surface states. 

The first theory of Auger effect was given by G. Wentzel (1927) in his seminal work on nonradiative quantum jumps [4], Wentzel used hydro-genic bound-state functions and the asymptotic forms of the free electron... 

Quantum-electrodynamics (QED) as the fundamental theory for electromagnetic interaction seems to be well understood. Numerous experiments in atomic physics as well as in high energy physics do not show any significant discrepancy between theoretical predictions and experimental results. The most striking example of agreement between theory and experiment represents the g factor of the free electron. The experimental value of g = 2.002 319 304 376 6 (87) [1] is confirmed by the calculated value of g = 2.002 319 304 307 0 (280) on the 10 11-level, where the fine structure constant as an input in the theoretical calculation was taken from the quantum Hall effect [2], Up to now uncalculated non-QED contributions play no important role. Indeed today experiment and theory of the free electron yield the most precise fine structure constant. 

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