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Band theory of the electronic properties of solids

W hat is the the ory of band? Solution to the Schrdinge r e quation for a pe riodic pote ntial Populating bands by e le ctrons. m e tals and non-m e tals C om pute r calculations ab initio band structure The evolution of the electronic structure of the periodic table of elements in the crystalline state. Sum m ary: possibilitie s and lim its of band the ory

5th EVOLUTION OF ELECTRON STRUCTURE ELEMENTS OF PROGRESS in the crystalline state

Explanation of the structure of the periodic table Mendeleev is one of the most important results of quantum mechanics and is presented in almost all of its manual. The repetition of similar physical and chemical properties of elements due to the subsequent filling subshells 1 s , 2 s , 2 p , etc.. with increasing atomic number. Here we will present an analysis of the periodicity manifested in the structure of electronic and physical properties of elements not present in the form of individual atoms, but solidified in the crystal. For definiteness, we will describe the evolution of the proceeds for periods 4 and 5 (containing the 18 elements), then we will present briefly the situation in other periods.

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De signe d by: R afa Kosture k

Figure 5.1. Periodic table of elements.

(I) simple metals of Groups IA and IIA metals begin Periodic alkaline Li, Na, K, Rb, Cs and Fr, can have an atomic valence electron in one state s . S orbitals are non-directional, which contributes to the fact that the properties are well described by an isotropic electron gas model of free electrons. Only alkali Fermi surface is roughly a sphere , nowhere in contact with the walls of the Brillouin zone and dealing with exactly half the volume. As shown by the dotted line in Figure 5.2b (potassium K) state density function D ( E ) up to the Fermi level coincides approximately with the relationship calculated using a model of free electrons. candidate IA column to the metallic state is hydrogen. On Earth, this element creates a diatomic molecule, which at low temperature condensation gives insulating molecular crystal. Hypothetical metallic properties of hydrogen are well known for a long time (fcc network, density = 0.57 g / cm 3 , B = 110 GPa, etc.). The difficulty of estimating the theoretical pressure needed to make it due to the uncertainty of calculations for high-pressure phases of hydrogen dwuatomowego. After a hundred years of trying the existence of metallic hydrogen has been, it seems, confirmed experimentally in 1996. It is believed that metallic hydrogen is
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seems, confirmed experimentally in 1996. It is believed that metallic hydrogen is present in the interior of the planets Jupiter and Saturn.

Figure 5.2a Schematic depiction of the creation of bands and their filling period for the four metals of the periodic table.

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Band theory of the electronic properties of solids

Figure 5.2b density of states functions for potassium (metal straight), vanadium (a transition metal), zinc (metal straight) and germanium (semiconductor).

For simple metal or alkaline earth include (column II). For these metals deviation from the model of free electrons is significant, in particular for beryllium. Metals columns IA and IIA groups include the simple metals . Metals in the periodic table also include a simple lies much further to the right column metals IB, IIB, IIIA, and IVA which will tell later. Figure 5.2a shows the qualitative nature of the band structure of simple metals in relation to the transition. Namely, the atomic 3s level extends in a broad band of quasi-free electrons. However, situated above the level of 3d extends in a smaller band width. For simple metal Fermi level of the two groups are respectively below and above the empty a filled band in full 3D. (ii) a transition metal in contrast to simple metals in transition metal band formed with atomic level 3 d , 4 d and 5 d ( respectively in the periods 4, 5 and 6) is filled in partially. On the density of states curve "type d "differs significantly from the" nearly free electron band "by the presence of a" comb "sharp maxima and minima which van Hove singularities (Figure 5.2b, also 4.6 ). Electronic structure calculations indicate that the bandwidth decreases with increasing d Z (4d metal group, for example, 8.3 eV to 6 eV and Zr to Pd), and increased when moving from the metal 3d 4d 5d (in a column containing Ni, Pd and Pt, respectively 4.5, 6 and 8 eV). Macroscopically, the transition metals are characterized by: higher melting points and fixed elasticity, lower electrical conductivity and generally lower reflectivity compared to the simple metals. Stronger "bound" transition metal atoms is a direct consequence of the completely filled up with the band d . It may be semi-quantitatively calculated as follows. Suppose that the level of atomic d containing n d electrons (1 < n d <9) expands symmetrically in band width in a constant (for simplicity) a function of the density of states. Cohesive energy is the product of this assumption, the displacement of center of gravity relative to the atomic state filled 3d level, equal to (W / 2) (1 - n / 10), and the number of electrons n . We get

(5.1) This primitive calculation explains semiquantitatively two facts: (i) is the maximum energy for a cohesive band d filled up to about half, and (ii) is proportional to its width, so that increases in the transition from the metal 3d 4d 5d. Among the elements 5d find examples of metals largest cohesive energy values (osmium, 788 kJ / mol), compressibility modulus (osmium, 418 GPa), density (osmium, 22.6 g / cm 3 ) and the melting point (tungsten, 3695 K) .

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Figure 5.3. cohesive energy values, Wigner-Seitz radius, and the compressibility modulus of metals 4 and 5, the order of the periodic table. (Wigner-Seitz radius is the radius of a sphere with a volume equal to the volume of the primitive cell is proportional to the size of the lattice constant). Legend: results of calculations for non-magnetic metals, including hypothetical nonmagnetic Cr, Mn, Fe, Co and Ni, the results for the magnetic elements, the experimental value. By. Calculated ... .

Dispersion relations for bands like "d" is more "flat" on the band 's ( figure 4.5 ). This means that the smaller the curvature (d 2 E / dk 2 ) and consequently ( solution. 2.3f ) larger effective mass several times greater than the free electron mass. It is one of the reasons that the transition metals conduct electricity worse than simple metals. The relatively low bandwidth 3d favors the appearance of magnetism (see chap. 4.5 ). Among the ferromagnetic 3d transition metals are Fe, Co and Ni, and Mn and Cr antyferromagnetykami. None of the elements 4d and 5d does not have a magnetic arrangement, next appearance of ferromagnetism is palladium. "Lability" of the electronic structure of this element is the cause of its excellent catalytic properties. There are also some ferromagnetic metal compounds 4d, eg ZrZn 2 . (iii) simple metals of groups IB - IVB After full bandwidth d Fermi level is located at the back of the subband dispersion curves similar to those of free electrons ( Fig. 4.5 ). The values the Fermi energy, D ( E F ) , and other electronic properties of the of second group of metals can be a simple model of the well to calculate the free electrons or free almost assuming that the metals of columns IB, IIB, IIIA and IVA are effectively one, two, three, and four electrons valence, ie, we ignore the impact of the 10 electrons filled up with the band d . This second group of metals simple column starts precious metals Cu, Ag and Au. The presence of band 3 d "submerged" quite shallow below the Fermi level explains why only this group of metallic elements has a distinct color. Consider an example of copper. The distance from the top edge of the band d to the Fermi level is about 1.6 eV ( Fig. 4.5 and 4.6 ). Photons with energy significantly greater (from green to purple) make the transition of electrons from the band "d" to empty states above the Fermi level, therefore, are quite strongly absorbed. However, the photons 'red' and 'orange' reflect almost 100%, making the characteristic color of the metal. Analogous to the silver distance increases to 3.2 eV, which is why it is absorbed only extreme violet, which explains the warm-silver color of the metal, different from the fully srebrzystobiaego gloss aluminum and zinc. The addition of zinc to copper causes an increase in the number of electrons per cell and consequently raising the Fermi level. The result is a yellow color of Cu-Zn alloy or brass. For simple column IIB metal (Zn, Cd, Hg) 3d band is "pushed" deep below the Fermi level ( Figure 5.2b , Zn) and metals are silvery white back. In group III metals (Ga, In, Tl) and roots band d IVB group is already very narrow and breaks away from the band nearly free electrons, moving at an atomic level of the spinal cord. (iv) semiconductors elements IVB columns show the diversity of the electronic properties. Lead and tin are metals with simple white, carbon in the form of graphite - semi-metal, and elements crystallizing in the structure of the diamond - a diamond C, Si, Ge and Sn gray - are semiconductors. Width (oblique) is the energy gap, respectively, 5.4, 1.1, 0.7, and 0.2 eV, therefore, decreases with increasing Z (v) semimetals heavier elements of column V of the Periodic Table: As, Sb and Bi are pmetalami . By semi-metal metal mean a very small (compared to the conventional metal), the density of states at the Fermi surface. Figure 5.4 shows an example Bi, why this is happening. Bi band structure is similar to a semiconductor with an inclined stop energy, for which the top of the valence band is 23 meV above the bottom of the conduction band. As a result, created "pockets" and the piercing of the electron concentration equal to n e = n h = 3.10 17 cm -3 , which is about 0.001 electron per atom. Among the elements of the periodic table is also a semi-metal graphite, the most common form of carbon. Intermetallic conductivity determines the number of applications of this material (carbon resistors, electrodes for primary batteries and electric arc furnaces, brush motors and generators).

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Figure 5.4. Bi band structure near the Fermi level obtained using relativistic ab initio calculations.

(Vi) insulating elements located further to the right are naog insulators for which the utility is limited by the band theory. Semiconducting property has only amorphous selenium. evolution outlined above electronic structure as a whole is carried out at 4 and 5-th row of the periodic table. Rows 2 and 3 of the 8 major elements, and of course in the first period is not electron d , so that there is a transition metal. Period 6th and 7th elements contain up to 32 due to the presence of orbitals 4 f , 5 f . Filling these orbitals leads to the formation of groups in the periodic table of rare earths and actinides.

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