Paulis Model

In Pauli s model, the sea of electrons, known as the conduction electrons are taken to be non-interacting and so the total wavefunction is just a product of individual one-electron wavefuncdons. The Pauli model takes account of the exclusion principle each conduction electron has spin and so each available spatial quantum state can accommodate a pair of electrons, one of either spin. 

In the Pauli model of paramagnetism, the conduction electrons are considered essentially to be free and under an applied field an imbalance between electrons with opposite spin is set up leading to a low magnetization in the same direction as the applied field. The susceptibility is independent of temperature, although the electronic band structure may be affected, which will then have an effect on the magnitude of the susceptibility. 

The corresponding fiinctions i-, Xj etc. then define what are known as the normal coordinates of vibration, and the Hamiltonian can be written in tenns of these in precisely the fonn given by equation (AT 1.69). witli the caveat that each tenn refers not to the coordinates of a single particle, but rather to independent coordinates that involve the collective motion of many particles. An additional distinction is that treatment of the vibrational problem does not involve the complications of antisymmetry associated with identical fennions and the Pauli exclusion prmciple. Products of the nonnal coordinate fiinctions neveitlieless describe all vibrational states of the molecule (both ground and excited) in very much the same way that the product states of single-electron fiinctions describe the electronic states, although it must be emphasized that one model is based on independent motion and the other on collective motion, which are qualitatively very different. Neither model faithfully represents reality, but each serves as an extremely usefiil conceptual model and a basis for more accurate calculations. 

The resolution of this issue is based on the application of the Pauli exclusion principle and Femii-Dirac statistics. From the free electron model, the total electronic energy, U, can be written as... 

Figure A3.13.14. Illustration of the quantum evolution (pomts) and Pauli master equation evolution (lines) in quantum level structures with two levels (and 59 states each, left-hand side) and tln-ee levels (and 39 states each, right-hand side) corresponding to a model of the energy shell IVR (liorizontal transition in figure...

For two and three dimensions, it provides a erude but useful pieture for eleetronie states on surfaees or in erystals, respeetively. Free motion within a spherieal volume gives rise to eigenfunetions that are used in nuelear physies to deseribe the motions of neutrons and protons in nuelei. In the so-ealled shell model of nuelei, the neutrons and protons fill separate s, p, d, ete orbitals with eaeh type of nueleon foreed to obey the Pauli prineiple. These orbitals are not the same in their radial shapes as the s, p, d, ete orbitals of atoms beeause, in atoms, there is an additional radial potential V(r) = -Ze /r present. However, their angular shapes are the same as in atomie strueture beeause, in both eases, the potential is independent of 0 and (j). This same spherieal box model has been used to deseribe the orbitals of valenee eleetrons in elusters of mono-valent metal atoms sueh as Csn, Cun, Nan and their positive and negative ions. Beeause of the metallie nature of these speeies, their valenee eleetrons are suffieiently deloealized to render this simple model rather effeetive (see T. P. Martin, T. Bergmann, H. Gohlieh, and T. Lange, J. Phys. Chem. 6421 (1991)). 

I will refer to the Hartree model from time to time in the text. Hartree s energies were in poor agreement with experiment. With the benefit of hindsight he should have allowed for indistinguishability and the Pauli principle. This was Fock s contribution to the field he wrote the wavefunction as what we would now recognize as a Slater determinant. Such a wavefunction automatically satisfies the Pauli principle. 

In Pauli s model, we still envisage a core of rigid cations (metal atoms that have lost electrons), surrounded by a sea of electrons. The electrons are treated as non-interacting particles just as in the Drude model, but the analysis is done according to the rules of quantum mechanics. 

Now, N/L is the number density of conduction electrons and so Pauli s model gives a simple relationship between the Fermi energy and the number density of electrons. If I follow normal practice and write the number density po then we have... 

It is now known that the view of electrons in individual well-defined quantum states represents an approximation. The new quantum mechanics formulated in 1926 shows unambiguously that this model is strictly incorrect. The field of chemistry continues to adhere to the model, however. Pauli s scheme and the view that each electron is in a stationary state are the basis of the current approach to chemistry teaching and the electronic account of the periodic table. The fact that Pauli unwittingly contributed to the retention of the orbital model, albeit in modified form, is somewhat paradoxical in view of his frequent criticism of the older Bohr orbits model. For example Pauli writes,... 

This theorem follows from the antisymmetry requirement (Eq. II.2) and is thus an expression for Pauli s exclusion principle. In the naive formulation of this principle, each spin orbital could be either empty or fully occupied by one electron which then would exclude any other electron from entering the same orbital. This simple model has been mathematically formulated in the Hartree-Fock scheme based on Eq. 11.38, where the form of the first-order density matrix p(x v xx) indicates that each one of the Hartree-Fock functions rplt y)2,. . ., pN is fully occupied by one electron. 

This result must now, however, be replaced by one based upon the quantum theory. In this case a generally applicable expression cannot be obtained, and it is necessary to consider particular molecular models. W. Pauli, Jr.3 has treated the diatomic dipole, which is of interest to us, and his treatment forms the basis of this discussion. 

Ng, K.L., Pauli, B., Haddad, P.R., and Tanaka, K., Retention modeling of electrostatic and adsorption effects of aliphatic and aromatic carboxylic acids in ion-exclusion chromatography, /. Chromatogr. A, 850, 17, 1999. 

The mutual electrostatic repulsion of the electrons and the Pauli repulsion between electrons having the same spin. The Pauli repulsion contributes the principal part of the repulsion. It is based on the fact that two electrons having the same spin cannot share the same space. Pauli repulsion can only be explained by quantum mechanics, and it eludes simple model conceptions. 

In this chapter we give a brief review of some of the basic concepts of quantum mechanics with emphasis on salient points of this theory relevant to the central theme of the book. We focus particularly on the electron density because it is the basis of the theory of atoms in molecules (AIM), which is discussed in Chapter 6. The Pauli exclusion principle is also given special attention in view of its role in the VSEPR and LCP models (Chapters 4 and 5). We first revisit the perhaps most characteristic feature of quantum mechanics, which differentiates it from classical mechanics its probabilistic character. For that purpose we go back to the origins of quantum mechanics, a theory that has its roots in attempts to explain the nature of light and its interactions with atoms and molecules. References to more complete and more advanced treatments of quantum mechanics are given at the end of the chapter. 

Although the Pauli principle seems to be a very abstract concept, we do in fact have direct experience of it because it is responsible for the solidity of matter. According to our model of an atom in which a certain number of very small electrons are moving around a very tiny nucleus, it would appear that most of the space around the nucleus is empty. However, because of the Pauli principle, in any region of space... 

Before discussing the AIM theory, we describe in Chapters 4 and 5 two simple models, the valence shell electron pair (VSEPR) model and the ligand close-packing (LCP) model of molecular geometry. These models are based on a simple qualitative picture of the electron distribution in a molecule, particularly as it influenced by the Pauli principle. 

We see that it is a consequence of the Pauli principle and bond formation that the electrons in most molecules are found as pairs of opposite spin—both bonding pairs and nonbonding pairs. The Pauli principle therefore provides the quantum mechanical basis for Lewis s rule of two. It also provides an explanation for why the four pairs of electrons of an octet have a tetrahedral arrangement, as was first proposed by Lewis, and why therefore the water molecule has an angular geometry and the ammonia molecule a triangular pyramidal geometry. The Pauli principle therefore provides the physical basis for the VSEPR model. 

The VSEPR model was originally expressed in these terms, but because Pauli repulsions are not real forces and should not be confused with electrostatic forces, it is preferable to express the nonequivalence of electron pairs of different kinds in terms of the size and shape of their domains, as we have done in this chapter. 

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