The Brillouin Zone

The state of an electron in a periodic crystal lattice can be described by a Bloch plane wave 

The wave vector k appearing in (4.18) can always be confined to the first Brillouin zone in reciprocal lattice. The first Brillouin zone has a fe-space volume 

In Table 4.1 we present the symbols denoting the points and crystal directions in the first Brillouin zone for a number of the most important crystal lattices. Such points and directions are of a high symmetry and play an important role in the computation of the vibration spectrum and the electronic band-structure of the 

Lattice Point Description Symbols of direction Crystal direction 

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Because (k) = (k + G), a knowledge of (k) within a given volume called the Brillouin zone is sufficient to detennine (k) for all k. In one dimension, G = Imld where d is the lattice spacing between atoms. In this case, E k) is known once k is detennined for -%ld < k < %ld. (For example, m the Kronig-Peimey model (fignre Al.3.6). d = a + b and/rwas defined only to within a vector 2nl a + b).) In tlnee dimensions, this subspace can result in complex polyhedrons for the Brillouin zone. 

In fignre A1.3.9 the Brillouin zone for a FCC and a BCC crystal are illustrated. It is a connnon practice to label high-synnnetry point and directions by letters or symbols. For example, the k = 0 point is called the F point. For cubic crystals, there exist 48 symmetry operations and this synnnetry is maintained in the energy bands e.g., E k, k, k is mvariant under sign pennutations of (x,y, z). As such, one need only have knowledge of (k) in Tof the zone to detennine the energy band tlnoughout the zone. The part of the zone which caimot be reduced by synnnetry is called the irreducible Brillouin zone. 

Figure C2.16.5. Calculated plots of energy bands as a function of wavevector k, known as band diagrams, for Si and GaAs. Indirect (Si) and direct (GaAs) gaps are indicated. High-symmetry points of the Brillouin zone are indicated on the wavevector axis.

Fig. 3.16 The efect of introducing a weak potential into the ID lattice is to lift the degeneracy of the energy levels mar to the edge of the Brillouin zone (shown in both extended-zone and reduced-zone representation).

Fig. 3.17 The two possible sets of standing waves at the Brillouin zone boundary. Standing wave A concentrates electron density at the nuclei, whereas wave B concentrates electron density between the nuclei. Wave A thus has a lower energy than wave B.

I be second important practical consideration when calculating the band structure of a malericil is that, in principle, the calculation needs to be performed for all k vectors in the Brillouin zone. This would seem to suggest that for a macroscopic solid an infinite number of ectors k would be needed to generate the band structure. However, in practice a discrete saaipling over the BriUouin zone is used. This is possible because the wavefunctions at points... 

Once the phonon frequencies are known it becomes possible to determine various thermodynamic quantities using statistical mechanics (see Appendix 6.1). Here again some slight modifications are required to the standard formulae. These modifications are usually a consequence of the need to sum over the points sampled in the Brillouin zone. For example, the zero-point energy is ... 

In Equation (5.58) the outer summation is over the p points q which are used to sample the Brillouin zone, is the fractional weight associated with each point (related to the volume of Brillouin zone space surrounding q) and vi are the phonon frequencies. In addition to the internal energy due to the vibrational modes it is also possible to calculate the vibrational entropy, and hence the free energy. The Helmholtz free energy at a temperature... 

The electronic structure of an infinite crystal is defined by a band structure plot, which gives the energies of electron orbitals for each point in /c-space, called the Brillouin zone. This corresponds to the result of an angle-resolved photo electron spectroscopy experiment. 

Simply doing electronic structure computations at the M, K, X, and T points in the Brillouin zone is not necessarily sufficient to yield a band gap. This is because the minimum and maximum energies reached by any given energy band sometimes fall between these points. Such limited calculations are sometimes done when the computational method is very CPU-intensive. For example, this type of spot check might be done at a high level of theory to determine whether complete calculations are necessary at that level. 

Calculations for Ceo in the LDA approximation [62, 60] yield a narrow band (- 0.4 0.6 eV bandwidth) solid, with a HOMO-LUMO-derived direct band gap of - 1.5 eV at the X point of the fee Brillouin zone. The narrow energy bands and the molecular nature of the electronic structure of fullerenes are indicative of a highly correlated electron system. Since the HOMO and LUMO levels both have the same odd parity, electric dipole transitions between these levels are symmetry forbidden in the free Ceo moleeule. In the crystalline solid, transitions between the direct bandgap states at the T and X points in the cubic Brillouin zone arc also forbidden, but are allowed at the lower symmetry points in the Brillouin zone. The allowed electric dipole... 

Fig. 6. Self-consistent band structure (48 valence and 5 conduction bands) for the hexagonal II arrangement of nanotubes, calculated along different high-symmetry directions in the Brillouin zone. The Fermi level is positioned at the degeneracy point appearing between K-H, indicating metallic behavior for this tubule array[17. ...

Wang wa used. The total energies were converged to 0.1 mRy/atom. The number of k points was chosen so as to correspond to 120 points in the irreducible wedge of the Brillouin zone of the fee structure, the energy cut-off was 16 Ry. We have tested various values of these parameters and it turned out that the present choice is sufficient to achieve desired uniform accuracy for all structures. For each structure the total energy was minimized with respect to the lattice constant. These interaction parameters correspond to the locally relaxed parameters and are denoted by superscript CW. 

The results of calculations for the points F—27r/a(0, 0,0) and A —27r/a(0,0.5,0) of the Brillouin zone are listed in Table 1. It can be seen that the energy eigenvsdues differ, on the average, by S Q Ryd between the two csdculations. Such an accuracy is quite sufficient for most applications. The qualitative picture of the electron spectrum is in complete agreement with our previous SPRKKR calculation. 

It is easy to see that this expression has two minima within the Brillouin zone. One minimum is at fc = 0 and gives the correct continuum limit. The other, however, is at k = 7t/a and carries an infinite momentum as the lattice spacing a 0. In other words, discretizing the fermion field leads to the unphysical problem of species doubling. (In fact, since there is a doubling for each space-time dimension, this scheme actually results in 2 = 16 times the expected number of fermions.)... 

According to a factor group analysis of R (space group I4cm with Z = 4), vibration modes can be presented in the center of the Brillouin zone (wave... 

Finally, this type of analysis can be carried out for any point in the Brillouin zone such that by using the transformation properties of spin waves and the character tables, one may obtain the spin-wave band structure throughout the zone. 

The reciprocal lattice is useful in defining some of the electronic properties of solids. That is, when we have a semi-conductor (or even a conductor like a metal), we find that the electrons are confined in a band, defined by the reciprocal lattice. This has important effects upon the conductivity of any solid and is known as the "band theory" of solids. It turns out that the reciprocal lattice is also the site of the Brillouin zones, i.e.- the "allowed" electron energy bands in the solid. How this originates is explciined as follows. 

Condition (2) is also quite common. For instance, in crystals it results in a reduced sound velocity, v q) when q approaches a boundary of the Brillouin zone [93,96], a direct result of the periodicity of a crystal lattice. In addition, interaction between modes can lead to creation of soft mode with qi O and corresponding structural transitions [97,98]. The importance of nonlocality at fluid interfaces and the corresponding softening of surface modes has been demonstrated recently, both theoretically [99] and experimentally [100]. 

The region within which k is considered (—n/a first Brillouin zone. In the coordinate system of k space it is a polyhedron. The faces of the first Brillouin zone are oriented perpendicular to the directions from one atom to the equivalent atoms in the adjacent unit cells. The distance of a face from the origin of the k coordinate system is n/s, s being the distance between the atoms. The first Brillouin zone for a cubic-primitive crystal lattice is shown in Fig. 10.11 the symbols commonly given to certain points of the Brillouin zone are labeled. The Brillouin zone consists of a very large number of small cells, one for each electronic state. 

The pictures in Fig. 10.12 give an impression of how s orbitals interact with each other in a square lattice. Depending on the k values, i.e. for different points in the Brillouin zone, different kinds of interactions result. Between adjacent atoms there are only bonding... 

In a cubic-primitive structure (a-polonium, Fig. 2.4, p. 7) the situation is similar. By stacking square nets and considering how the orbitals interact at different points of the Brillouin zone, a qualitative picture of the band structure can be obtained. 

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