Computational Chemistry: A Practical Guide for Applying Techniques to Real-World Problems.

David C. Young
Copyright ( 2001 John Wiley & Sons, Inc.
ISBNs: 0-471-33368-9 (Hardback); 0-471-22065-5 (Electronic)

34 Band Structures

In molecules, the possible electronic energies are discrete, quantized energy

levels. As molecules become larger, these energy levels move closer together.
In a crystal, the energy levels have merged together so closely that they are
continuous bands of available energies for all practical purposes. Thus, the
electronic structure of a crystal is described by its band structure.

34.1 MATHEMATICAL DESCRIPTION OF ENERGY BANDS

The electronic structure of an in®nite crystal is de®ned by a band structure plot,

which gives the energies of electron orbitals for each point in k-space, called the
Brillouin zone. This corresponds to the result of an angle-resolved photo elec-
tron spectroscopy experiment.
k-space is not a physical space. It is a description of the bonding nature of
orbitals. In an in®nitely long string of atoms, the phases of orbitals might be
anywhere from all bonding to all antibonding (these extremes are labeled as
k ˆ 0 and k ˆ p=a). Somewhere in between are combinations with three atoms
in a row oriented for bonding, followed by an antibonding one or any other
such combination. As k-space is de®ned, k ˆ 0 corresponds to complete bond-
ing symmetry for some orbitals and complete antibonding for others, depend-
ing on the symmetry of the atomic orbitals.
k-space will have three dimensions …kx ; ky ; kz † for three-dimensional crystals.
Certain points in k-space are given names. The designator G refers to the point
where k ˆ 0 in all dimensions. M is the point with k ˆ p=a in all directions. X,
Y, K, and A are points with k ˆ 0 in some directions and k ˆ p=a in others,
depending on the symmetry of the crystal. The typical band structure plot,
called a spaghetti plot, maps the orbital energies along the paths between these
points, as shown in Figure 34.1. These designations are discussed in more detail
in the literature cited in the bibliography.
As orbitals spread into bands, orbitals oriented for s or s  bonds spread into
the widest bands. p orbitals form narrower bands and d bonding orbitals form
the narrowest bands.

34.2 COMPUTING BAND GAPS

In some cases, researchers only need to know the band gap for a crystal. Once a
complete band structure has been computed, it is, of course, simple to ®nd the
266
 34.2 COMPUTING BAND GAPS 267

100

80

60

40
Energy (eV)

20

-20

-40
Z Γ X M R Γ
FIGURE 34.1 Band-structure plot for CoNb4 Si.

band gap by inspection. However, computing the entire band structure could
involve an extensive amount of work to obtain a lot of unneeded information.
There are ways of estimating the band gap, although these are not completely
reliable.
Simply doing electronic structure computations at the M, K, X, and G points
in the Brillouin zone is not necessarily su½cient 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 some-
times done when the computational method is very CPU-intensive. For exam-
ple, this type of spot check might be done at a high level of theory to determine
whether complete calculations are necessary at that level.
Some researchers use molecule computations to estimate the band gap from
the HOMO±LUMO energy separation. This energy separation becomes smaller
as the molecule grows larger. Thus, it is possible to perform quantum mechan-
ical calculations on several molecules of increasing size and then extrapolate the
energy gap to predict a band gap for the in®nite system. This can be useful for
polymers, which are often not crystalline. One-dimensional band structures are
268 34 BAND STRUCTURES

also used for such systems, thus assuming crystallinity or at least a high degree
of order.

34.3 COMPUTING BAND STRUCTURES

Since ab initio and semiempirical calculations yield orbital energies, they can be
applied to band-structure calculations. However, if it is time-consuming to cal-
culate the energy for a molecule, it is even more time-consuming to calculate
energies for a list of points in the Brillouin zone. Since these calculations are
so computationally intensive, extended HuÈckel has been the method of choice
unless more accurate results are needed. In the realm of band-structure calcu-
lations, extended HuÈckel is sometimes called the tight binding approximation.
In recent years, there has been an increasing tendency to use ab initio or DFT
methods.
Like molecular calculations, an ab initio method requires both a set of basis
functions and a means for computing the energy. The choice of basis sets for
band structure calculations is somewhat di¨erent than for molecular calcu-
lations. Large basis sets with di¨use functions can contain contractions having
a large overlap, with their image in the adjacent unit cell. When this happens, it
creates a linear dependency that prevents the self-consistent equations from
being solved. Most often, small- to medium-size basis sets are used to avoid this
problem. The linear combination of atomic orbitals (LCAO) scheme used for
molecular calculations can be applied to crystal calculations, but it is not the
only option. Actually, the basis functions centered on atoms are formed into
Bloch functions, which obey the translational symmetry of the system, although
the term LCAO is still used.
Another basis technique that is popular for modeling crystals is the use of
plane wave basis functions. Plane waves were proposed because they re¯ect
the in®nite symmetry of a crystal. There have been several di¨erent plane
wave techniques proposed. The earliest plane wave calculations assumed the
SchroÈdinger equation was spherically symmetric in a region around each atom
(dubbed a mu½n tin potential), but su¨ered from an inability to conserve
charge. These mu½n tin calculations gave reasonable results for ionic crystals.
They are no longer performed since algorithms and computer hardware im-
provements make more accurate and reliable calculations feasible. A technique
still used is the augmented plane wave (APW) technique, which is a cellular
calculation over the Vigner±Seitz cell. There are many other basis function
methods that are used for certain types of problems.
Band structure calculations have been done for very complicated systems;
however, most of software is not yet automated enough or su½ciently fast that
anyone performs band structures casually. Setting up the input for a band
structure calculation can be more complex than for most molecular programs.
The molecular geometry is usually input in fractional coordinates. The unit cell
lattice vectors and crystallographic angles must also be provided. It may be nec-
 34.4 DESCRIBING THE ELECTRONIC STRUCTURE OF CRYSTALS 269

essary to provide a list of k points and their degeneracies. It is safest to check

the convergence of any input option a¨ecting the calculation accuracy. Manuals
accompanying the software may give some suggested values. Researchers
wishing to complete band structure calculations should expect to put a lot of
time into their e¨orts particularly during the learning stage for the software to
be used.
As mentioned above, the preferred computational methods for modeling
crystals have changed over the years. Below is a list of basis function schemes,
with the most often used appearing ®rst:

1. Linear combination of atomic orbitals (LCAO)

2. Augmented plane wave method (APW)
3. Green's function method of Korringa, Kohn, and Rostoker (sometimes
denoted KKR)
4. Orthogonalized plane wave (OPW)
5. Pseudopotential method
6. Various approximate or empirical methods

Any orbital-based scheme can be used for crystal-structure calculations. The

trend is toward more accurate methods. Some APW and Green's function
methods use empirical parameters, thus edging them toward a semiempirical
classi®cation. In order of preference, the commonly used methods are:

1. Self-consistent ab initio or DFT methods

2. Semiempirical methods
3. Methods using an ad hoc or model potential

34.4 DESCRIBING THE ELECTRONIC STRUCTURE OF CRYSTALS

The population analysis techniques used for molecular calculations are not
directly applicable to band structure calculations. A series of techniques for
analyzing the band structure have been introduced. These are generally pre-
sented as graphical plots. The data for these plots come from a series of calcu-
lations at various points in k-space. Very good plots can be obtained by calcu-
lating a very large number of points. In order to reduce computer time, a more
widely spaced set of points can be generated; then the plots are smoothed by
some kind of interpolation algorithm. It is always prudent to perform several
calculations with points increasingly close together to see if the plot changes
signi®cantly.
One important question is how many orbitals are available at any given
energy level. This is shown using a density of states (DOS) diagram as in Figure
34.2. It is typical to include the Fermi level as denoted by the dotted line in this
®gure. A material with a half-®lled energy band is a conductor, but it may be a
270 34 BAND STRUCTURES

20

10
Energy (eV)

10

20

30
0 2 4 6 8 10 12

DOS
FIGURE 34.2 Density of states plot for CoNb4 Si.

very poor conductor if there are very few un®lled orbitals available. In some
cases, the contributions of a particular orbital to the DOS are plotted on the
same graph as a shaded region or dotted line.
Another question is whether the ®lled orbitals are of a bonding or anti-
bonding character. This is displayed on a crystal orbital overlap population
(COOP) plot as shown in Figure 34.3. Typically, the positive bonding region is
plotted to the right of the zero line.
The Fermi energy is the energy of the highest-energy ®lled orbital, analogous
to a HOMO energy. If the orbital is half-®lled, its energy will be found at a
collection of points in k-space, called the Fermi surface.

34.5 COMPUTING CRYSTAL PROPERTIES

There has not been as much progress computing the properties of crystals as
for molecular calculations. One property that is often computed is the bulk
modulus. It is an indication of the hardness of the material.
It may be desirable to predict which crystal structure is most stable in order
to predict the products formed under thermodynamic conditions. This is a very
di½cult task. As of yet, no completely automated way to try all possible crystal
structures formed from a particular collection of elements (analogous to a
molecular conformation search) has been devised. Even if such an e¨ort were
attempted, the amount of computer power necessary would be enormous. Such
studies usually test a collection of likely structures, which is by no means infal-
 BIBLIOGRAPHY 271

20

10
Energy (eV)

10

20

30
0.5 0.4 0.3 0.2 0.1 0 0.1 0.2

COOP
FIGURE 34.3 Crystal orbital overlap plot for CoNb4 Si.

lible. Energy minimizations can be performed, provided that the starting struc-
ture has the correct symmetry.

34.6 DEFECT CALCULATIONS

Sometimes, the system of interest is not the in®nite crystal, but an anomaly in the
crystal, such as an extra atom adsorbed in the crystal. In this case, the in®nite
symmetry of the crystal is not rigorously correct. The most widely used means
for modeling defects is the Mott±Littleton defect method. It is a means for per-
forming an energy minimization in a localized region of the lattice. The method
incorporates a continuum description of the polarization for the remainder of
the crystal.

BIBLIOGRAPHY

Text books describing band structures are

P. Y. Yu, M. Cardone, Fundamentals of Semicondutors Springer-Verlag, Berlin
(1996).
272 34 BAND STRUCTURES

R. Ho¨mann, Solids and Surfaces A Chemist's View of Bonding in Extended Structures

VCH, New York (1988).
I. M. Tsidilkovski, Band Structure of Semiconductors Pergamon, Oxford (1982).
W. A. Harrison, Solid State Theory Dover, New York (1979).
A. A. Levin, Solid State Quantum Chemistry McGraw-Hill, New York (1977).
Orbital Theories of Molecules and Solids N. H. March, Ed., Clarendon, Oxford (1974).
J. C. Slater, Quantum Theory of Molecules and Solids McGraw-Hill, New york (1963).

Review articles are

J. K. Burdett, J. Phys. Chem. 100, 13274 (1996).
C. R. A. Catlow, J. D. Gale, R. W. Grimes, J. Solid State Chem. 106, 13 (1993).
E. Canadell, M.-H. Whangbo, Chem. Rev. 91, 965 (1991).
J. H. Harding, Rep. Prog. Phys. 53, 1403 (1990).
C. R. A. Catlow, G. D. Price, Nature 347, 243 (1990).
JCS Faraday Trans. II Vol. 85, part 5 (1989).
R. Ho¨mann, Angew. Chem. Int. Ed. Engl. 26, 846 (1987).
C. R. A. Catlow, Ann. Rev. Mater. Sci. 16, 517 (1986).
J. C. Slater, Adv. Quantum Chem. 1, 35 (1964).

The program used to create the ®gures is YAeHMOP, which has two main
executables, which are
G. A. Landrum, W. V. Glassey, Bind 3.0 (1998).
G. A. Landrum, Viewkel 2.0 (1998).
both at http://overlap.chem.cornell.edu:8080/yaehmop.html