Electronic Band Structure Fundamental Theory and Methods: A Review

Abstract: Electronic band structure is indispensible for determining properties of crystalline materials both qualitatively and quantitatively. Band structures are represented by E vs k diagrams and corresponding calculations are carried out in the framework of single particle approximation. This review discusses the construction of single particle equations and various methods (tight binding approximation, cellular method, APW and OPW methods) that have been developed for solving these equations. Review concludes with the discussion of electronic structure of different representative solids. Introduction: Electronic band structure of a crystal determines the allowed and forbidden energies of electrons in a solid. Graphically, it is represented as E vs k diagrams. For three dimensional materials, it is not possible to plot one graph for all values of k. Therefore, k is chosen to lie along lines that join high symmetry points in the first Brillouin Zone (BZ) of the reciprocal space. For example, free electron E vs k diagram in reduced-zone scheme for an fcc lattice (with 2 electrons per atom) is shown in Figure 1[1]. Inset shows first BZ with conventional notation for points of symmetry.

Figure:2: BZ and band structure of hypothetical 2D crystal with 1 atom, 4 orbitals / PUC

Single Particle Approximation: Band structure calculations operate within the singleparticle framework [3] which can be developed by considering various approximations on many-body Schrodinger equation of the solid. Schrodinger equation of the solid is:
(* +) (* +)

Figure:1: Free electron band structure for fcc lattice

where is the many body wave function and Hamiltonian of the solid is given by:
| | | |

This scheme can also be used for two dimensional crystals though it is possible to plot one three dimensional graph for all values of k. BZ for a square lattice with symmetry points and shaded triangle representing irreducible BZ is shown in Figure 2 [2]. Band structure of a hypothetical 2D crystal with one atom (and 4 orbitals) per primitive unit cell (PUC) is also shown. The importance of band structure is because of its fundamental role in explaining behavior and properties of solids. The basic information provided by E vs k diagrams is whether a material is conductor, insulator or semiconductor. Electrical and magnetic properties can be predicted by these graphs. Minimum energy crystal structures can also be calculated from the information provided by band structure [3].

The first two terms in the Hamiltonian represent kinetic energies of all ions and valence electrons in the solid, respectively. Third, fourth and fifth terms correspond to electron-electron, electron-ion and ion-ion interactions in the solid, respectively. Because of huge difference in masses of ions and electrons, ions can be considered to be stationary so that the wave function depends only on electronic degrees of freedom. This is called BornOppenheimer approximation because of which first term in the above Hamiltonian can be neglected. The last term can also be ignored because it consists of ion-ion interactions which are constant when only considering electronic degrees of freedom. The Hamiltonian of the solid, thus, takes the form:

( )

where
( ) | |

Single particle Hartee equations can be solved by using a computational iterative technique starting from a set of single particle states. This approach is necessary because solving equation for each requires information about rest of the states in the set * +. Hartee approximation ignores the fermionic nature of electrons. In Hartee Fock approximation, many-body wavefunction of the solid is assumed to have the form of wavefunction of a system with N non-interacting fermionic particles: ( ) ( ) ( ) ( ) ( ) ( ) ( ( ( ) )

is the potential energy of an electron due to interaction with all ions in the solid. Hamiltonian developed so far still contains summation over variables of all electrons. The difficulty in solving for such a Hamiltonian lies in the exchange and correlation properties of electrons [2]. Exchange property implies that proper wavefunction of the system should be antisymmetric because if spatial variable of two electrons of same spin is changed, wavefunction must change sign. Correlation property represents inter-dependence of electrons motion because each electron affects the motion of every other electron in the solid. The Hamiltonian with summation over variables of all electrons can be simplified further by considering Hartee approximation, Hartee-Fock approximation or density functional theory. In Hartee approximation, many-body wavefunction of the solid is assumed to have the form of wavefunction of a system with N non-interacting particles: (* +) ( ) ( ) ( )

(* +)

This determinant (known as Slater determinant) assures that the wavefunction is anti-symmetrized. Here are normalized single particle states and N is the total number of electrons. Using the same variational approach as discussed above for Hartee approximation, single particle Hartee-Fock equations are obtained:
[ ( ) ( )] | ( ) | | | ( ) ( )

where are normalized single particle states and N is the total number of electrons. Total energy of the system is then given by: | | By using constraint of normalized wavefunction and introducing Lagrange multipliers , variational argument results in single particle Hartee equations:

This equation is same as that for Hartee approximation except for the last exchange term which represents the effect of fermionic nature of electrons. Another approach to solving the many-body Schrodinger equation is to formulate the problem in terms of total density of electrons ( ). This approach is called Density Functional Theory and its basic ideas were developed by Hohenberg, Kohn and Sham [4, 5]. Total density of electrons ( ) is such that there is a one-to-one correspondence between electron density and external potential for electrons. This implies that wavefunction is a unique functional of density. Total energy of the system is given by:

( )

( )

( )

( )

( )]

( )

( )

| | |

where
( ) | | | |

Here T and W represent the kinetic energy contribution and electron-electron interaction contribution to the total energy, respectively. V is the external potential for electrons.

is the Hartee potential.

Using F to represent the combined contribution from kinetic energy and electron-electron interaction, total energy of the system takes the form: | | , ( )| | ( ) ( )

F does not depend on V and it is a universal functional for all systems of N particles. If F is obtained then any particular form of V can be added to it and resulting sum can be minimized to obtain electron density [4], thus solving the Schrodingers equation. Unfortunately, exact form of F is not known and it has to be replaced with various approximations. One approach to the problem is to write electron density in terms of single particle states: ( ) | ( ) |

Figure:3: Real wave function and Coulomb potential (left). Pseudo-state and potential (right)

Tight Binding Approximation: Tight binding approximation is also referred to as LCAO (Linear combination of atomic orbitals). In this method, crystal wave functions are expanded in terms of orbitals that are very similar to atomic orbitals.
( )

( )

( )

Starting from total energy of the system: | | And using variational argument, single particle equations called Kohn-Sham equations are obtained: [ with ( ) |
( ) | , ( )( )

where ( ) is the crystal basis constructed from orthogonal atomic orbitals ( ) and it satisfies Blochs theorem. For atomic orbital, l is the angular momentum character and ti represents orbitals position in PUC. Using these crystal wave functions, single particle equation takes the form: [ | |
( )

( ))]

( )

( )

Here Veff is the effective potential and EXC is the potential term that contains all the exchange, correlation effects. Band Structure Methods: Before solving single particle equations obtained above, the ionic potential to be used in these equations needs to be specified. In a solid, core electrons wave functions remain practically unchanged and main contribution in bonding comes from valence electrons. The core electrons crowd the nucleus and screen it from outside. Apseudopotential can be constructed that takes into account these properties of core and valence electrons. Corresponding to this pseudopotenial are the pseudo-valence states that are smoother near the nucleus but preserve the nature of real valence states away from core region. Schematic representation of pseudo-valence states and potential is shown in Figure 3 [2].

where is the single particle Hamiltonian. This secular equation can be solved to obtain eigenenergies and coefficients in expansion of crystal wave functions. While solving the Hamiltonian matrix elements, it is usually approximated that only nearest neighbors contribute and other matrix elements are zero. Symmetry of atomic orbitals is used to simplify the calculation of matrix elements. Besides explicitly calculating Hamiltonian matrix elements, these can be considered as parameters that are fitted to reproduce known properties of a crystal and then used to calculate the unknown properties. Cellular or Linearized Muffin Tin Orbital (LMTO) Method: In this method, solid is considered to be made up of Wigner-Seitz (WS) cells which are a special type of PUC. Within each cell, there is a spherical region in which the potential experienced by the electrons is spherically

symmetric. A schematic representation for a hexagonal WS cell is shown in Figure 4 [1].

Such orthogonalized trial valence states are then used as a basis for expanding true valence states. OPW method was developed by C. Herring [8]. Band Structure of Representative Solids: Band structures of representative solids will be discussed here. The calculated structures are obtained using PPW (Pseudopotential plane wave method) [2]. Semi-metal

Figure:4: WS cell and spherical potential in LMTO method

Because of spherical nature of potential, wave functions can be expanded in spherical harmonics and radial functions: ( ) ( ) ( )

Using these wave functions in single particle equation gives a secular equation which can be solved to obtain the eigenenergies. The boundary conditions satisfied by these wave functions at the boundary of WS cell are: ( ( ) ( ) ) ( ( ) ) ( )

Figure:5: Band structure of graphene and its BZ

where (

) is the vector normal to surface of WS cell.

This LMTO method was developed by Wigner and Seitz [6]. Augmented Plane Waves (APW) Method: This method uses the same concept of dividing the solid into spherical and interstitial regions as used in LMTO. In spherical region, wave functions are expanded in terms of functions with spherical symmetry and outside the spherical region wave functions are expanded in terms of plane waves. The two wav functions should match at the spherical boundary. This method was first developed by Slater [7]. Orthogonalized Plane Waves (OPW) Method: In this method, trial wave functions for valence states is expanded in terms of both plane waves and core waves where the core wave functions are obtained from atomic cores and satisfy Blochs theorem. Parameters are chosen so that trial valence states are orthogonal to core states.

Graphene is a 2D, single layer, sp2 hybridized carbon with honey comb lattice. The BZ of graphene is hexagonal and band structure along particular directions in k space is shown in Figure 5. Considering the shape of band structure at point, it is clear that lowest band has s-character from bonding of s orbitals. Third and fourth bands have pcharacter coming from bonding of two p orbitals. pz orbitals contribute towards the second band. There are two atoms per unit cell and four orbitals per atom. This means that four bands will be completely filled in the BZ. Below Fermi-energy, marked in Figure 5, all the bands are fully occupied at zero temperature. At P point in the band structure, VBM (valence band maximum) and CBM (conduction band minimum) touch each other. This implies that graphene is a semi-metal. Semi-conductor & Insulator

Figure:6: Band structure of Silicon (with VBM at zero)

Silicon and Carbon have diamond crystal structure (i.e. two interpenetrating fcc lattices with a two atom basis). BZ of

these structures is bcc as shown in Figure 1. There are 8 valence electrons per PUC which means that four bands will be completely filled in the BZ. Band structures of Si and C with VBM at zero, are shown in Figures 6 and 7 respectively. The range of energies for which no band is present across the entire BZ is called the band gap. Existence of band gap is property of insulators and semiconductors. Both C and Si have indirect band gap because VBM and CBM are present at different points in BZ. Band gaps for C and Si (as shown in Figures 6 and 7) are 5 and 1.2 eV. The range of energies occupied by valence band is called band width. Band widths of C and Si (as shown in Figures 6 and 7) are 23 and 12.5 eV. In both C and Si, valence electrons participate in sp3 hybridization. Lowest band at for both solids has an s-character. The next three band at point have p-character from three p orbitals. The s and p like character become less prominent away from the point.

Figure:8: Band structure of Aluminum (with Fermi level at zero)

Figure:9: Band structure of Silver (with Fermi level at zero)

References: 1. 2. 3. 4. 5. Physics of Solids - Eleftherios N. Economou Atomic and Electronic Structure of Solids Efthimios Kaxiras Condensed Matter Physics Michael P. Marder Inhomogeneous Electron Gas - P. Hohenberg, W. Kohn Phys. Rev. (1964) Self-Consistent Equations Including Exchange and Correlation Effects W. Kohn, L. J. Sham Phys. Rev. (1965) On the Constitution of Metallic Sodium - E. Wigner, F. Seitz -Phys. Rev. (1933) Wave Functions in a Periodic Potential - J. C. Slater - Phys. Rev. (1937) A New Method for Calculating Wave Functions in Crystals - Conyers Herring - Phys. Rev. (1940)

6.
Figure:7: Band structure of Carbon (with VBM at zero)

7. 8.

Metal Al and Ag have fcc structure with 1 atom per PUC. Their band structures, marked with Fermi-level, are shown in Figures 8 and 9. Both of the solids have free electron/ almost perfect parabolic character at point. Al has two valence electrons which means that on average 1.5 bands will be occupied throughout BZ. Ag has five valence electrons which means that on average 5.5 bands will be occupied throughout BZ. For both solids, there is no gap between VBM and CBM. This is characteristic of conducting materials. Electrons can cross the Fermi level through thermal excitations.