Crystalline Solids Band Theory

Crystalline Solids Band Theory 530 Key Learning Outcomes 534... 

Band theory provides a picture of electron distribution in crystalline solids. The theory is based on nearly-free-electron models, which distinguish between conductors, insulators and semi-conductors. These models have much in common with the description of electrons confined in compressed atoms. The distinction between different types of condensed matter could, in principle, therefore also be related to quantum potential. This conjecture has never been followed up by theoretical analysis, and further discussion, which follows, is purely speculative. 

Diffusion and migration in solid crystalline electrolytes depend on the presence of defects in the crystal lattice (Fig. 2.16). Frenkel defects originate from some ions leaving the regular lattice positions and coming to interstitial positions. In this way empty sites (holes or vacancies) are formed, somewhat analogous to the holes appearing in the band theory of electronic conductors (see Section 2.4.1). 

The above simple picture of solids is not universally true because we have a class of crystalline solids, known as Mott insulators, whose electronic properties radically contradict the elementary band theory. Typical examples of Mott insulators are MnO, CoO and NiO, possessing the rocksalt structure. Here the only states in the vicinity of the Fermi level would be the 3d states. The cation d orbitals in the rocksalt structure would be split into t g and eg sets by the octahedral crystal field of the anions. In the transition-metal monoxides, TiO-NiO (3d -3d% the d levels would be partly filled and hence the simple band theory predicts them to be metallic. The prediction is true in TiO... 

For many years, during and after the development of the modem band theory of electronic conduction in crystalline solids, it was not considered that amorphous materials could behave as semiconductors. The occurrence of bands of allowed electronic energy states, separated by forbidden ranges of energy, to become firmly identified with the interaction of an electronic waveform with a periodic lattice. Thus, it proved difficult for physicists to contemplate the existence of similar features in materials lacking such long-range order. 

The Band Theory of Crystalline Solids. Consider a crystalline solid. The atoms are arranged according to a three-dimensional pattern (or lattice) in which they have equilibrium interatomic distances. A thought experiment is now performed. The lattice is expanded, i.e., the interatomic distances are increased. 

In crystalline organic solids such as anthracene, in which the mobility is on the order of 1 cm2/Vs, the transport mechanism may still be explained by a band theory formalism. But for most organic solids (especially if disordered), the mobility values are far below the lower limit value and a hopping transport mechanism seems to be more appropriate. Organic polymers are classic examples of hopping transport materials. In poly-iV-... 

Some of the discussion of bonding theory will concern distorted crystals or crystals with defects then description in terms of bond orbitals will be essential. Description of electronic states is relatively simple for a perfect crystalline solid, as was shown for CsCl in Chapter 2 for these, use of bond orbitals is not essential and in fact, in the end, is an inconvenience. We shall nevertheless base the formulation of energy bands in crystalline solids on bond orbitals, because this formulation will be needed in other discussions at the point where matrix elements must be dealt with, we shall use the LCAO basis. The detailed discussion of bands in Chapter 6 is done by returning to the bonding and antibonding basis. 

The electronic structure of solids and surfaces is usually described in terms of band structure. To this end, a unit cell containing a given number of atoms is periodically repeated in three dimensions to account for the infinite nature of the crystalline solid, and the Schrodinger equation is solved for the atoms in the unit cell subject to periodic boundary conditions [40]. This approach can also be extended to the study of adsorbates on surfaces or of bulk defects by means of the supercell approach in which an artificial periodic structure is created where the adsorbate is translationally reproduced in correspondence to a given superlattice of the host. This procedure allows the use of efficient computer programs designed for the treatment of periodic systems and has indeed been followed by several authors to study defects using either density functional theory (DFT) and plane waves approaches [41 3] or Hartree-Fock-based (HF) methods with localized atomic orbitals [44,45]. 

Phase Diagrams (P versus T) 13-14 Amorphous Solids and Crystalline Solids 13-15 Structures of Crystals 13-16 Bonding in Solids 13-17 Band Theory of Metals... 

Describe the three types of cubic unit cells and explain how to find the number of particles in each and how packing of spheres gives rise to each calculate the atomic radius of an element from its density and crystal structure distinguish the types of crystalline solids explain how the electron-sea model and band theory account for the properties of metals and how the size of the energy gap explains the conductivity of substances ( 12.6) (SP 12.4) (EPs 12.57-12.75)... 

In the previous chapters, we discussed various models of bonding for covalent and polar covalent molecules (the VSEPR and LCP models, valence bond theory, and molecular orbital theory). We shall now turn our focus to a discussion of models describing metallic bonding. We begin with the free electron model, which assumes that the ionized electrons in a metallic solid have been completely removed from the influence of the atoms in the crystal and exist essentially as an electron gas. Freshman chemistry books typically describe this simplified version of metallic bonding as a sea of electrons that is delocalized over all the metal atoms in the crystalline solid. We shall then progress to the band theory of solids, which results from introducing the periodic potential of the crystalline lattice. 

In summary, the band theory of solids can be used to explain the structure, spectroscopy and electrical properties of one-dimensional solids, such as the linear chain tetracyanoplatinates. However, most crystalline solids have translational symmetry in more than one dimension. Can band theory be extended to two and even three dimensions The answer is, of course, yes. However, the shapes of the bands become significantly more complicated as the number of dimensions increases. Let us just consider two dimensions for the moment and an imaginary lattice composed of only H atoms. In two dimensions, the wavefunction for the Bloch orbitals is given by Equation (I 1.27) ... 

The valence bond theory is useful in explaining the structure and the geometry of molecules, but it is not suitable to explain the properties of semiconductor materials. The energy-band model for electrons can be applied to all crystalline solids and allows identifying a conductor, an insulator or a semiconductor material. Indeed, the properties of a solid are determined by the difference of energy between the different bands and the distribution of the electrons contained within. 

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