Brillouin zone, first

Vgiec and Vxc represent the electron-nuclei, electron-electron and exchange-correlation dionals, respectively. The delta function is zero unless G = G, in which case it has lue of 1. There are two potential problems with the practical use of this equation for a croscopic lattice. First, the summation over G (a Fourier series) is in theory over an rite number of reciprocal lattice vectors. In addition, for a macroscropic lattice there effectively an infinite number of k points within the first Brillouin zone. Fortunately, e are practical solutions to both of these problems. 

Figure 3.27. The first Brillouin zone of the facc-ccntrcd cubic structure, after Pippard.

It is known that a metallic ID system is unstable against lattice distortion and turns into an insulator. In CNTs instabilities associated two kinds of distortions are possible, in-plane and out-of-plane distortions as shown in Fig. 8. The inplane or Kekuld distortion has the form that the hexagon network has alternating short and long bonds (-u and 2u, respectively) like in the classical benzene molecule [8,9,10]. Due to the distortion the first Brillouin zone reduees to one-third of the original one and both K and K points are folded onto the F point in a new Brillouin zone. For an out-of-plane distortion the sites A and B are displaced up and down ( 2) with respect to the cylindrical surface [11]. Because of a finite curvature of a CNT the mirror symmetry about its surface are broken and thus the energy of sites A and B shift in the opposite direction. 

G. Herzberg, Molecular Spectra and Molecular Structure, Vol. II - Infrared and Raman Spectra of Polyatomic Molecules, Van Nostrand Reinhold, New York, 1945 In the crystalline state, it is more convenient to speak about multi-phonon processes since the modes from the whole dispersion range of the first Brillouin zone are allowed to contribute according to the conservation of energy and momentum of the phonons involved in the process... 

The matrices A, B, Q are of infinite dimension since there are an infinite number (2N+1, N — oo) of k-values and thus an infinite number of k-states in each band. Moreover, there is an equation for each triplet formed by a k-value and two band indices. This triplet represents a particle-hole excitation that is vertical in order to preserve the momentum. As is the case in many polymeric techniques, the infinite sum over k is transformed into an integration in the first Brillouin zone ... 

Figure 4 Conduction band levels and excitation levels of infinite periodic hydrogen chains by using different approximations of the polarization propagator. The left part refers to the crystalline orbital energy differences, namely, the Hartree-Fock excitation energies the right part refers to the random phase approximation results obtained by using 41 k-points in half the first Brillouin zone.

The orbitals <]) j(k r) are Bloch functions labeled by a wave vector k in the first Brillouin zone (BZ), a band index p, and a subscript i indicating the spinor component. The combination of k and p. can be thought of as a label of an irreducible representation of the space group of the crystal. Thequantity n (k)is the occupation function which measures... 

In the case of a perfect crystal the Hamiltonian commutes with the elements of a certain space group and the wave functions therefore transform under the space group operations accorc g to the irreducible representations of the space group. Primarily this means that the wave functions are Bloch functions labeled by a wave vector k in the first Brillouin zone. Under pure translations they transform as follows... 

A Bloch function for a crystal has two characteristics. It is labeled by a wave vector k in the first Brillouin zone, and it can be written as a product of a plane wave with that particular wave vector and a function with the "little" period of the direct lattice. Its counterpart in momentum space vanishes except when the argument p equals k plus a reciprocal lattice vector. For quasicrystals and incommensurately modulated crystals the reciprocal lattice is in a certain sense replaced by the D-dimensional lattice L spanned by the vectors It is conceivable that what corresponds to Bloch functions in momentum space will be non vanishing only when the momentum p equals k plus a vector of the lattice L. 

The region within which k is considered (—n/a 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. 

First Brillouin zone for a cubic-primitive crystal lattice. The points X are located at k = it/a in each case... 

A theoretical interpretation relating the valence electron concentration and the structure was put forward by H. Jones. If we start from copper and add more and more zinc, the valence electron concentration increases. The added electrons have to occupy higher energy levels, i.e. the energy of the Fermi limit is raised and comes closer to the limits of the first Brillouin zone. This is approached at about VEC = 1.36. Higher values of the VEC require the occupation of antibonding states now the body-centered cubic lattice becomes more favorable as it allows a higher VEC within the first Brillouin zone, up to approximately VEC = 1.48. 

Figure 7. The occupation number densities as functions of wave vector for Na. The thick curves labeled (100), (110) and (111) represent the three principal directions within the first Brillouin zone, obtained by the FLAPW-GWA. The thin solid curve is obtained from an interacting electron-gas model [27]. The dash-dotted line represents the Fermi momentum. 

In the left panel of Figure 8 we show the band structure calculation of graphite in the repeated zone scheme, together with a drawing of the top half of the first Brillouin zone. The band structure is for the 1 -M direction. As the dispersion is very small along the c-axis we would find a similar result if we add a constant pc component to the line along which we calculate the dispersion [17]. The main difference is that the splitting of the a 1 and % band, caused by the fact that the unit cell comprises two layers, disappears at the Brillouin zone boundary (i.e. if the plot would correspond to the A-L direction). 

A comparison of the band structure diagram and these two measurements shows that experimentally the main measured intensity is constrained to a few of the bands present. In the first Brillouin zone the ct, band is found to be occupied, in the second zone 02. No sign of o, or the % band is found for the T M measurement. For the A-L measurement the same bands as for the T-M measurement contribute but in addition the n band is observed, mainly in the first Brillouin zone. These experiments are a beautiful, direct observation of the nodal plane of the % electrons in momentum space. 

In this chapter we will have a closer look at the methods of the reconstruction of the momentum densities and the occupation number densities for the case of CuAl alloys. An analogous reconstruction was successfully performed for LiMg alloys by Stutz etal. in 1995 [3], It was found that the shape of the Fermi surface changed and its included volume grew with Mg concentration. Finally the Fermi surface came into contact with the boundary of the first Brillouin zone in the [110] direction. Similar changes of the shape and the included volume of the Fermi surface can be expected for CuAl [4], although the higher atomic number of Cu compared to that of Li leads to problems with the reconstruction, which will be examined. 

One can clearly see the large positive anisotropy in the [111] direction near the boundary of the first Brillouin zone (BZB). It is caused by the [111] high momentum component, which produces a continuous distribution of the momentum density across the BZB, as the Fermi surface has contact with the BZB in this direction. In the other directions, especially in [100], calculations show a steep decrease of the momentum density at the Fermi momentum and therefore a negative deviation from the spherical mean value. 

Figure 4. Momentum density anisotropy of Cu the solid line marks the boundary of the first Brillouin zone solid and dashed contour lines mark positive and negative anisotropies, respectively.

The conclusion to be drawn from Eq. (37) is thfit the volume of the first Brillouin zone is equal to the reciprocal of file volume of the primitive cell. It should be noted that the scalar product... 

Here uf = u exp(277ig r) is, like w, periodic with the period of the lattice, and k = k - 27rg is a reduced wave vector. Repeating this as necessary, one may reduce k to a vector in the first Brillouin zone. In this reduced zone scheme, each wave function is written as a periodic function multiplied by elkr with k a vector in the first zone the periodic function has to be indexed, say ujk(r), to distinguish different families of wave functions as well as the k value. The index j could correspond to the atomic orbital if a tight-binding scheme is used to describe the crystal wave functions. 

Luttinger-Tisza method is burdened by independent minimization variables, while analysis of the values of the Fourier components F k) makes it possible to immediately exclude no less than half of the variable set and to obtain a result much more quickly. Degeneracy of the ground state occurs either due to coincidence of minimal values of Vt (k) at two boundary points of the first Brillouin zone k = b]/2 and k = b2/2, or as a result of the equality Fj (k) = F2 (k) at the same point k = h/2. The natural consequence of the ground state degeneracy is the presence of a Goldstone mode in the spectrum of orientational vibrations.53... 

Fig. 2.9. Ground state for a square lattice of dipoles a. Orientations of dipole moments b. wave vectors of the structure in the first Brillouin zone c. and d. orientations of dipole moments in infinitely small and large external electric fields, respectively.

The expansion of Fourier components of the dipole interaction tensor in the vicinity of the minimum point at the boundary of the first Brillouin zone, with the Cartesian axes Ox and Oy respectively chosen along bi and b2 (see Fig. 2.9b), has the form... 

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