(Solid State Physics) Volume 7 - Electron Energy Bands in Solids by Callaway, Joseph (1958)

Electron Energy Bands in Solids
JOSEPHCALLAWAY
Department of Physics. University of Miami. Coral Gables. Florida
.
I Introduction and General Theory., ................................... 100
1. The Energy Band ................................................ 100
2. The Many-Electron Problem ...................................... 101
3. The Hartree-Fock Equations., .................................... 104
4. The Crystal Potential ............................................ 106
5. Symmetry Properties ............................................. 108
6. Behavior of a Band near B Degeneracy ............................. 111
.
7 The Density of States ............................................ 113
8. Normal Form of an Energy Band .................................. 115
9. Methods of Calculation ........................................... 118
I1. The Alkali Metals .................................................. 119
.
10 General Discussion............................................... 119
11. Determination of the Fermi Energy ................................ 121
12. Crystal Potentials for the Alkali Metals ............................ 123
13. Core Polarization ................................................ 125
14. Relativistic Effects ............................................... 126
15. Lithium ........................................................ 128
16. Sodium ......................................................... 133
17. Potassium ...................................................... 136
18. Rubidium and Cesium ............................................ 140
19. The Knight Shift ................................................ 143
20. Metallic Hydrogen ............................................... 145
.
21 General Survey and Conclusions................................... 146
I11. Metals of Groups I1 and I11......................................... 147
22. General Diacussion ............................................... 147
.
23 Beryllium ....................................................... 148
.
24 Magnesium ..................................................... 151
25. Calcium ........................................................ 154
26. Aluminum ...................................................... 154
27. Solid Helium .................................................... 158
.
IV Elements of Group IV and Related Semiconductors..................... 158
28. General Considerations........................................... 158
29. Graphite ........................................................ 159
30. Diamond ....................................................... 164
31. Silicon .......................................................... 168
32. Germanium ..................................................... 172
33. Tin, Indium Antimonide, and Indium Arsenide ...................... 176
.
34 Gallium Arsenide................................................ 179
99
100 JOSEPH CALLAWAY
V. The Transition Metals.. ............................................ 180

35. General Considerations.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
36. Experimental Information. .
37. Titanium.................
38. Chromium........................
39. Iron ......................
40. Nickel.. . . . ........... ...........
41. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
VI. Other Substances. .... .............................. 19i
42. Silver and Gold. ... ....................... 197
43. Tungsten..................... ....................... 198
44. Bismuth .......... .............................. 198
45. Selenium and Tellurium.. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
46. Alkali Halides: Sodium Chloride.. .....................
47. Potassium Chloride. ............... ..............
48. Lithium Rydride and Lithium Fluoride.. . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
49. Lead Sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
50. Zinc Sulfide . . . . . . . . . . . . . . . . .... 208
51. Barium Oxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
52. Miscellaneous Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
VII. Conclusions and Prospects.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
1. Introduction and General Theory

I
1. THEENERGY BAND
A convenient assumption to make in beginning the discussion of the
behavior of electrons in crystals is that we may consider the motion of only
one particle in a periodic potential. This is an oversimplification, for one
really has a many-electron problem. Moreover, real crystals are not per-
fectly periodic but contain imperfections. Some of the complications
which arise because of the many-particle nature of the problem will be
discussed in subsequent sections; a general treatment of the problem of
imperfections is beyond the scope of this review. With this simplifying
assumption mentioned above, Bloch proved that solutions of Schrod-
inger's equation have the form'
in which uk(r) is periodic in r with the periodicity of the potential. This

theorem is a general consequence of translational symmetry. The wave
functions are characterized by the wave number k which may be thought
of as equivalent t o the crystal momentum. The energy of a state g k de-
pends in a reasonably continuous fashion on the wave number. The rela-
tion between energy and wave number characterizes an energy band.
The simplifying assumptions made above could lead to the false im-
1 F. Bloch, 2.Physilc 62, 555 (1928).
ELECTRON ENERGY BANDS I N SOLIDS 101
pression that energy bands are found only in periodic structures. It is

still useful to talk about energy bands in a disordered material provided
the atoms are sufficiently close that the atomic wave functions of atoms
on neighboring sites overlap. In such a case, one part of the material is,
on the average, just like any other part, so that wave functions and
energy values can still be characterized by a reasonably continuous
dependence of energy on momentum. We will not expect however, that
Eq. (1.1) will hold in such circumstances.
It should be apparent that the E(k) relation is one of themmostimpor-
tant properties of a material. It is involved in a basic way in-any calcula-
tion of the electric, optical, or thermal characteristics of the substance.
The calculation of E(k) relations for actual materials is extremely compli-
cated. Many considerations of electrical properties, for example, are
based on extremely simplified models of the real band structure. Progress
has been made, however, in determining energy bands in a number of the
simpler metals and semiconductors. We shall describe, first of all, some
of the general features of energy bands in periodic lattices, and will then
discuss both theoretical and experimental results in materials which have
been subject to detailed study. There will be no discussions of artificial
models, such as the Kronig-Penney model, or of methods of calculation.
For a survey of these topics, the reader is referred to the reviews by
Reita and by Slater.2
2. THEMANY-ELECTRON
PROBLEM
The enormous number of particles involved in a typical solid makes
direct solution of the Schrodinger equation completely impossible, and
leads naturally to the development of a one-electron approximation. It is
necessary, however, to relate the one-electron theory to the actual many-
electron situation, and to estimate the corrections to the results of the
one-body approximation. One might well wonder at first how a one-parti-
cle approximation can have any validity in the case of electrons which
interact with reasonably strong and very long-range forces. Experience
does convince us, however, that it is quite useful. We will examine the
reason for this.
Suppose we have a set of one-particle wave functions believed to be
appropriate to the problem. The best choice of these functions will be
discussed in the next section. An antisymmetric N-body wave function
can be found by taking N of the one-particle functions and forming a
Slater determinant in the standard manner. Such an approximate wave
function for the system will be called a model function in this article. If
* J. R. Reitz, Solid State Physics 1, 1 (1955);J. C.Slater in “Handbuch der Physik,”
Vol. 19, p. 1. Springer, Berlin, 1956.
102 JOSEPH CALLAWAY
we construct all the possible N by N determinants out of the one-body

functions, the result is a complete set of antisymmetric N-body functions
in terms of which the real wave function of the system can be expanded.
It usually is convenient to choose the model functions to be eigen-
functions of a partial Hamiltonian which either does not include the
interactions between particles at all, or includes only the average of these
interactions. The model functions can then be considered as approximate,
or unperturbed wave functions, for the system and the difference between
the actual and model Hamiltonians can be treated as a perturbation.
The actual machinery of this perturbation theory is quite complex and
will not be discussed in detail here for the reason that the Coulomb inter-
action in metals (as well as many of the interactions of interest in nuclear
physics) apparently leads to infinite results. Procedures have been
devised which circumvent this difficulty.3~~
The question of principal concern to us is the relation between stand-
ard energy band theory and the many-body problem. It appears that
much of the basic language of the theory is unchanged. W. Kohn has
shown that the behavior of an extra electron or hole in an insulator can be
described in some circumstances by an effective mass e q ~ a t i o nA. ~more
general approach would seem to be afforded by the work of Bethe, Gell-
Mann, and Brueckner, etc.*s4The one-particle functions which are com-
bined to form the model wave function of standard energy band theory
satisfy Bloch's theorem and can be designated by the appropriate wave
vector and band index. A model wave function can be characterized by
specifying the one-particle states which are occupied. From a given model
state, a real state can be constructed. The actual energy of the system
can be associated with the model state from which the real state is de-
rived. It may not be possible, however, to obtain all the real states in this
way. In the model wave function of lowest actual energy Eo, the wave
vectors of the occupied one-electron states will lie within some surface in
k space. The excited states of interest to band theory are specified, in
relation to the ground-state model function, by listing the wave vectors
and spins of the previously occupied states which are now vacant (kl)and
the previously empty states now filled (hi"). (Here i = 1, . . . Y, where
Y is the number of excited particles or holes.) Let the real energy of an
* For a treatment of the general theory of the many-body problem see, for instance,
H. Bethe, Phys. Rev. 103, 1353 (1956), and the references contained therein.
4 The Coulomb interaction is treated by M. Gell-Mann and K. A. Brueckner, Phys.
Rev. 106, 364 (1957); M. Gell-Mann, Phys. Reu. 106, 369 (1957); K. Sawada, Phys.
Rev. 106, 372 (1957).
W. Kohn, Phys. Rev. 106, 509 (1957). For a general'discussionof the many-body
problem in solids see H. Haken, 2. Nuturforsch. Qa, 228 (1954).
ELECTRON ENERGY BANDS IN SOLIDS 103
excited state be E. Then we write (following Gell-Mann*):
E = Eo + Zi[W(ki’) - W(ki’)]+ O(U/N). (2.1)
The quantity W(ki”) is the difference in actual energy between the
ground state (Eo)and a state containing N +
1 particles, the additional
particle being (as far as the model wave function is concerned) in the
previously unoccupied state ki”. Here W(ki”) may be thought of as
representing the complete interaction energy of one particle in the state
k4’ with the rest of the system, but it differs quantitatively from a similar
quantity calculated in the Hartree-Fock approximation (see Section 3)
because of the more accurate inclusion of the correlation between particle
motions in this procedure. Similarly W(ki’) is the difference in energy
between the ground state and a state with N-1 particles, one particle
being removed from the previously occupied state ki’. In addition to the
quantities W(k), the energy of the excited N-body state must include
terms containing the interaction between excited particles and between
excited particles and holes. This interaction is of the order u/N, and can
be neglected if v / N is small.
In more physical terms, the many-body system is capable of single-
particle excitations, and also of other excitations, such as collective
oscillations,6which are not described easily in a single-particle model and
in which the interaction between the excited particles is important. The
interesting single-particle excitations are those whose energy is low com-
pared to a collective oscillation.
An energy band is specified by the function W(k).A description of the
many-body system in terms of energy bands will be meaningful formally
when the excitation energy is not too large (less than is required to excite
a collective oscillation) and as long 88 we are not concerned with the
interactions between excited particles and between excited particles and
holes. The energy bands defined in this way are the same as those obtained
from the Hartree-Fock equations (3.1) when the more detailed treatment
of the particle interactions is neglected. In general, however, there are
quantitative differences arising from the more detailed treatment of particle
interactions in W(k).
Experimental results seem to indicate that the basic ideas of the one-
particle approximation actually are applicable to metals.’ A well-defined
Fermi surface (the surface enclosing the occupied region of k space for
the one-particle functions) exists in metals and its characteristics can be
6 D. Pines, Sotid State Physics 1, 367 (1955). In a recent paper Noaihres and Pines
discussed the nature of the elementary excitations in solids. P. Nozi&resand D.
Pines, Phys. Rev. 109, 1062 (1958).
7 N. F. Mott, Nature 178, 1205 (1956).
104 JOSEPH CALLAWAY
determined. It also appears that many excitations of low-energy can be

described conveniently in terms of a one-particle model. This is quite
consistent with the point of view expressed in the foregoing. It should be
possible, and it is a basic objective of band theory to determine the shape
of the Fermi surface and to account quantitatively for the one-particle
excitations by computing the function W ( k ) .
Similar successes of the one-particle model are observed in semicon-
ductors. The reasons for success in this case are perhaps more obvious.
I n the first place, the number of holes and electrons involved in transport
processes is usually very small, so that it is quite reasonable to neglect
terms of the order v / N . Second, because of the existence of a finite energy
gap between filled and vacant states in the one-particle model, ordinary
perturbation theory of the electron interaction is convergenLs
3. THE HARTREE-FOCK EQUATIONS

Although a theory for finding the exact energy to be associated with a
model state exists, it has not yet been possible to make calculations for
real systems. All existing calculations of energy bands are based on the
use of one model function. The question then presents itself: what is the
best choice of a model function? This can be determined by use of the
variational principle. The best model function is that for which the expec-
tation value of the energy is a minimum, subject to the conditions that the
one-particle functions which compose it be orthonormal. We are lead in
this way to an equation for the oneparticle functions,2 namely, the
Hartree-Fock equations. Let such a one-particle function be ~(zj). The
equation is:
In the second term on the left, riL is the distance between electron i and
the nucIeus L (assumed fixed). The sum runs over all the nuclei of the
system. The third term expresses the average electrostatic potential of
all the electrons of the system and the fourth term is the exchange inter-
action. In the approximation of Koopmans’ t h e ~ r e mthe
, ~ energy parame-
ter ei measures, the energy required to remove an electron in state i from
the system. In other words it is the quantity W(k)for the Hartree-Fock
* C. W.Ufford, Phys. Rev. 69, 598 (1941).
9 T.Koopmans, Physica 1, 104 (1933).
approximation. The interpretation of this equation is discussed in the

reviews by Reitz and Slater.2
The calculation of energy bands is based, in principle, on the Hartree-
Fock equations. These equations form a quite complicated nonlinear
integro-differential system. It is clear that numerical methods of solution
must be employed. The usual procedure is the method of self-consistent
fields. At the outset, values for the functions ui are assumed. The integrals
appearing in the equations are calculated with the use of the starting
functions and the equations (which now have the standard Schrodinger
form for a single particle) are solved for the eigenvalues ei and the function
ui. If the solutions agree, within assigned limits, with the functions as-
sumed, the work is completed; if not, the process is repeated until such
time as the results of the nth and n +
1 stages agree. The procedure is
quite lengthy, and has been applied only to some of the simpler free
atoms.l0
In the case of a solid, there are two types of difficulties which stand in
the way of obtaining a self-consistent field calculation. Assume that a
choice of starting functions has been made, and the appropriate integrals
have been evaluated. Then Eq. (2.1) can be written effectively as
where V . and Vex are ordinary and exchange potentials respectively.

Vexmay depend on the state i under consideration. (See Section 4.)
It is then necessary to solve (3.1) for a sufficiently large number of states
that a reasonable idea of the band structure and wave functions can be
obtained. This problem is more difficult than for free atoms because cen-
tral symmetry does not prevail in solids. Thus the wave equation, in
general, cannot be separated. Certain methods have been devised which
will give good results, at least for some states. These methods are dis-
cussed in the review article of R e i k 2
Once the equations have been solved, the integrals must be re-evalu-
ated and the process repeated until self-consistency has been achieved.
This is quite difficult, in general, because it involves summing the charge
distribution over all occupied states. I n fact, the problem is so difficult
that self-consistent calculations have not been completed for solids except
possibly in the case of the alkali metals.
For the results to be meaningful, it is necessary that the potentials
employed in (3.1) be reasonably close to those which would result from a
self-consistent calculation. Physical arguments must be used.
10 D. R. Hartree, “The Calculation of Atomic Structures.” Wiley, New York, 1957.
106 JOSEPH CALLAWAY
It is apparent that the principal physical problem in a calculation band

structure is the choice of an appropriate crystal potential. Some of the
common approximations will be discussed in the next section. It is obvious
immediately that those results which depend critically on the details of
the potential used in a particular calculation must be viewed with some
caution. Moreover it is important to determine the features of a calcula-
tion which are likely to be sensitive to the potential.
4. THE CRYSTALPOTENTIAL
Since the construction of a crystal potential is of crucial importance
in a band calculation, it is desirable to discuss the various approximations
in more detail. In Eq. (3.2) the crystal potential was separated into two
parts; namely, an ordinary potential which is the sum of the nuclear
attractions and the averaged electronic repulsions, and an exchange
potential. The symmetry of the crystal permits us to calculate the poten-
tial within a single atomic cell. Consider first the ordinary potential. It is
convenient to separate this into two parts; namely, the potential arising
from the charge distribution in the particular cell, and that arising from
all the other cells. Since the computation of these requires a knowledge
of the charge distribution in the crystal, and hence the self-consistent
solution of the problem, certain approximations are made.
Consider first the case of a monatomic crystal. Each cell is electrically
neutral, so that we need to consider only one atom. In the solid state
problem we usually are concerned only with the valence electrons. The
core electron distributions on different atoms overlap very little, so that
bands of negligible width are formed. Thus it is legitimate to regard the
core electron distribution as the same in the solid and in the free atom.
For this reason any information we may have about the distribution of
the core electrons in the free atom is also relevant to the solid. Consider as
examples the alkali metals, in which there is one electron outside a core
of compact closed shells. Information regarding the core electron distribu-
tion may be obtained either from a self-consistent field calculation for the
free ion, or from the spectroscopic data for the free atom. In the latter
case, either an empirical potential can be constructed (see Section 12) or
spectroscopic information can be used almost directly and explicit con-
struction of a potential function can be avoided. For substances more
complicated than the alkali metals, one generally must rely on self-con-
sistent field calculations for the free atom in determining the core electron
distribution. It is very unfortunate that self-consistent fields are available
for less than half the atoms in the periodic table and that only a small
number of the calculations that have been made include exchange.ll
As a result of the assumptions which must be made concerning the
11 Existing SCF calculations are listed by R. S. %ox, Solid State Phys. 4,413 (1957).
valence electron distribution, the construction of the crystal potential is
uncertain. In the alkali metals, the Wigner-Seitz approximation (Section
10) allows us to avoid this difficulty by using the ionic potential. For
more complicated materials, some assumption must be made explicitly.
It is probably adequate in many metals to assume that the external elec-
trons are uniformly distributed. This is not allowable for d electrons in the
transition elements. In ionic crystals, one may assume free ions, and use
the charge distribution appropriate to them. There is no clearly satisfac-
tory procedure in valence semiconductors.
If the crystal being considered is not monatomic, there is the possi-
bility of ionic character, for each atomic cell need not be electrically neu-
tral. The potential within a particular cell will not be determined by the
charge within the particular cell alone under these conditions. The rest
of the lattice must be taken into account. This contribution can be esti-
mated if the charges of the ions are known. The constant term in this
potential can be determined easily from the lattice parameter, effective
charge, and the Madelung constant. This "Madelung" potential is not
actually constant in the unit cell; however, it has the symmetry of the
lattice, so that it is reasonable to neglect all but the constant part for
cubic crystals.
The determination of the exchange potential is still more uncertain.
Fortunately, this potential usually is reasonably small compared with the
ordinary potential and need not be determined with extreme accuracy.
Actually, an exchange potential is defined only in reference to a particular
state, and varies from state to state. For the function ui we define:
The sum runs only over states having the same spin as ui. It usually is
not practical to obtain different exchange potentials for all the electronic
states of interest in a band calculation. Slater has proposed certain simpli-
fying approximations which can be used to obtain an average exchange
potential for all states.I2A comparison of approximate exchange potentials
has been given by Herman, Callaway, and Acton.Ia The most celebrated
of these approximations replaces (4.1) by the exchange potential which
would exist in a free electron gas having the same density, namely:
1) J. C. Raterl Plcys. Rev. 81,385 (1951).

1* F. Herman, J. Callaway, and F. S. Acton, Phys. Rev. 96,371 (1954);see also V. W.
Maslen, Proc. Phys. SOC.(London) A M , 734 (1956), for further discussion.
108 JOSEPH CALLAWAY
Here p is the density of electrons having the same spin as the state con-
sidered and is a function of position. This expression seems to give a
reasonably faithful qualitative rendition of the results of (4.1) for many
states, but it is inaccurate quantitatively. [It may be noted here that we
must include j = i in (4.1).] It seems to over-estimate the effect of ex-
change by as much as 20 to 30% in some cases." Slater's more involved
average12does not seem to be appreciably better.18
A somewhat better approximation probably can be obtained by assum-
ing that the exchange potential is the same for all states having the same
angular momentum. I* States are not characterized by an angular momen-
tum quantum number in a solid; however, in discussing states at sym-
metry points of the Brillouin zone in simple metals, it will often be possi-
ble to characterize the states by the predominant angular momentum i'n
the expansion of the wave function in terms of spherical harmonics. It is
probably better not to average the exchange potential over all the states
of the free atom having the angular momentum considered, as proposed
in ref. 12, since such states are likely to be more tightly bound than those
of interest in the solid. It is more reasonable to construct approximate
wave functions and determine an exchange potential from them. One
drawback in the procedure of introducing an exchange potential is that
V,, will have infinities if the function ui in (4.1) has nodes. These infinities
actually contribute nothing to the energy, but must be removed by some
smoothing or averaging process if an exchange potential is to be used like
an ordinary potential.
The reader should be aware of the very considerable uncertainty that
is involved in a crystal potential. It is likely that this difficulty will not be
resolved satisfactorily until such time as it is possible to calculate a self-
consistent field for a solid on the basis of Eq. (3.1).
Even in cases in which the questions of the ordinary and exchange
potentials within an individual cell are settled, there remains the question
of the interactions of the free electrons in different cells with each other.
This interaction depends on the wave vector k and consequently needs to
be included in an energy band calculation. There is, however, no quantita-
tive way of doing this a t present.
5. SYMMETRY PROPERTIES
Because uncertainties exist in constructing a crystal potential, it is
desirable to employ symmetry considerations whenever possible to aid in
determining wave functions and energy levels. The classification of crystal
wave functions according to their symmetry properties is, of course, inde-
pendent of the detailed nature of the crystal potential. Such classification
I4J. Callaway, Phys. Rev. 99, 500 (1955).
will usually be found to be of considerable value in the calculational
process. Often symmetry considerations can be combined with experi-
mental data and simple theoretical inferences to derive quite reasonable
ideas of the bands in a particular crystal.
It is assumed that the reader is familiar with the basic ideas concerning
the symmetry properties of a crystal, in particular the Brillouin zone, as
discussed in standard texts.16 In this section the principles underlying the
symmetry classification of wave functions will be presented, based on
the work of Bouckaert, Smoluchowski, and Wigner.lBA detailed review of
these considerations has been given by Koster. l7 In subsequent sections,
the behavior of an energy band near a degeneracy will be discussed ( 6 ) ,
the application of topological results to the determination of the density
of states will be considered (7),and finally a normal form will be pro-
posed for separate bands in simple lattices (8).
In the Hartree-Fock approximation, each one-electron wave function
must transform according to some representation of the space group of
the crystal. Consider first the invariant subgroup formed by the transla-
tions. Since all the translations commute with each other and with the
Hamiltonian, the energy eigenfunctions are also eigenfunctions of the
translation operators. This statement is equivalent to Bloch’s theorem
and implies that the functions are characterized by a wave vector k. In
addition to the translations, there are other operations which are rota-
tions and reflections in the simplest cases. If such an operation is applied
to a wave function for a particular k, the latter will be transformed into a
function having a different wave vector k’, which arises from k by the
operation considered. All the k’formed from a general k,will be different;
however, the energy will be the same for each. For some values of k,
there will be symmetry operations which carry k into itself or into vector
k‘ = k -!- K for which K is a reciprocal lattice vector. Such operations
form a group, which is called the group of the wave vector. The wave func-
tion for such a k will transform, under the group of k, as an irreducible
representation of this group, called a small representation.
The small representations and their connections have been worked out
for the simple cubic, body-centered cubic, and face-centered cubic lattices
in ref. 15. The notation of this paper will be used throughout. The
hexagonal lattice and the diamond lattice have been considered by
Herring. ls The zincblende structure has been studied by Parmenterlg and
16 F. Seitr, “The Modern Theory of Solids.” McGraw-Hill, New York, 1940.

l6L. P. Bouckaert, R. Smoluchowski, and E. Wigner, Phys. Rev. 60, 58 (1936).
1’ G. F. Koster, Solid State Phys. 6, 173 (1957).
18 C. Herring, J . Franklin Inst. 233, 525 (1940); see also W. Doring and V. Zehler,
Ann. Phys. 18, 214 (1953).
19 R. H. Parmenter, Phys. Rev. 100, 573 (1955).
110 JOSEPH CALLAWAY
Dresselhaus.20Elliotta1has discussed the double group (spin included), as

have Parmenter and Dresselhaus. The reader is referred to these sources
for character tables. A general review of this material is given by Koster."
The utility of classifying the wave functions according to symmetry in
a band calculation is that the Hamiltonian has matrix elements only
between those functions which belong to the same row of the same irre-
ducible representation. Consequently, use of symmetrized functions is of
great value in diagonalizing the Hamiltonian. Modern methods of calcu-
lating energy bands employ expansions based on symmetrized functions.
The determination of the matrix elements of various operators is also
facilitated.
Symmetry considerations also furnish information concerning the
form and connections of the various bands in the Brillouin zone. Suppose
energy levels have been determined for a particular wave vector ko and
+
is desired to obtain the energies at a nearby wave vector ko s. As is well
+
known, the energies of states at ko s can be found from these at koby
determining the effect of the perturbation 2is V (see Section 7). Sym-
metry considerations are not particularly helpful if kois a general point in
+
the zone. If ko is a symmetry point, and (ko s) is a general point, all the
degeneracy which may have been present a t ko is removed. If the group
+
of (ko s) is a subgroup of the group of ko, but contains more than the
identity, as occurs on going away from k = 0 along a symmetry axis, the
+
wave functions a t (ko s) transform according to the subgroup. If the
appropriate representation of the group of ko is reducible as a representa-
+
tion of the subgroup at (ko s), the degeneracy at kowill be removed at
+
least in part. Of course, if the groups at ko and ko s are the same, the
degeneracy will be the same. The compatibility relations summarize this
information and express the way in which levels at symmetry points may
connect with the bands along symmetry axes. These relations are obtained
from the representations as indicated above, and are given in the refer-
ences already listed.
A degeneracy, or sticking together of energy bands can be required by
symmetry only when the wave vector ko is invariant under some sym-
metry operations. The problem of accidental degeneracy of energy bands
(degeneraciesnot required by symmetry) has been examined by Herring.22
It is almost impossible for bands having the same symmetry to cross. For
example, at a general point, two wave functions having the same wave
vector never have the same energy, so that energy bands do not cross at
a general point. Similarly, on a symmetry axis, bands of the same sym-
20 G.Dreeselhaus, Phys. Rev. 100, 580 (1955).
21 R.J. Elliott, Phy8. Reu. 96, 380 (1954).
** C. Herring, Phys. Rev. 62,365 (1937).
metry do not cross. Bands of unlike symmetry may cross, however. These
rules are important in determining bands away from symmetry points,
and when taken in conjunction with the known compatibility relations
and calculated values of energy levels at symmetry points, enable us in
many cases to derive qualitative ideas as to the form of energy bands in a
particular crystal.
6. BEHAVIORO F A BANDNEAR A DEGENERACY

Near a point of degeneracy in the band structure, a simple Taylor
series expansion of E(k) is not possible. The first investigation of this
question appears to have been made by Bowers.28The first published
account is that of Sh~ckIey.~*
The one-electron Schrodinger equation for a state $k, (including spin
orbit coupling but neglecting an explicit exchange interaction and rela-
tivistic effects other than spin orbit coupling) is:
The wave functions have the Bloch form #ko = eilr'J%,,. The function uk,,
satisfies the equation
The equation for k = ko + s is
The term
can be treated as a perturbation.

The solution of (6.3) according to ordinary second-order perturbation
*a W. A. Bowers, Ph.D. Thais, Cornell University, 1943 (unpublished).
24 W. Shockley, Phys. Rev. 78, 173 (1950).
112 JOSEPH CALLAWAY
theory is
Here
The superscript 0 indicates the state which is being perturbed and the
superscript y indicates any other state, including the core states for the
given ko.The operator
transforms a8 a vector. The solution (6.4) is valid only as long as Uk: is not
a member of a degenerate set; Eq. (6.4) is equivalent to a Taylor series
expansion of the energy about k. The first term in (6.4) gives rise to a
linear dependence of energy on wave vector going away from k. This
h e a r term vanishes for certain states a t symmetry points. In these cases
&(k) is quadratic in s near ko:and an analytic critical point (Section 7) is
formed. I n order for $uk;*H’uk: dT to be different from zero, it is neces-
sary that the integrand be a scalar. More precisely, the direct product
roX ro X r0 must contain rl, where I’l is the completely symmetric
representation of the group of k, r. is the representation of a vector, and
J?o is the representation to which Uk: belongs. All representations are the
same at a general point of the zone, and the linear dependence will gener-
ally exist. The linear term may vanish at symmetry points. For examples
V 8 = 0 for all representations at r, H , and N in the body-centered
cubic lattice.
If u k ; is a member of a degenerate set, the perturbation removes the
degeneracy. In the most important cases, the degeneracy is removed in
second order, and the perturbation theory appropriate for this case must
be used.26The energy is obtained as the solution of a secular equation, of
which the general element is
The indices i and j run over the members of the degenerate set and the
index y runs over all other states. The order of the equation is the degree
aSL. I. Schiff, “Quantum Meeh&nics,”2nd ed., p. 156. McGraw-Hill, New York, 1949.
of degeneracy of the set. The dependence of E on s, although generally
quadratic, is more complicated than given by (6.4) and can lead to com-
plicated, warped surfaces and nonanalytic critical points. The precise
forms of the energy surfaces which are degenerate at k = 0 are important
in the analysis of certain experiments on semiconductors, notably p-type
silicon, germanium, and indium antimonide. Semiempirical analyses of
the bands near k = 0 in these substances have been based on (6.5). (See
Sections 31, 32, and 33.)
7. THE DENSITY
OF STATES
It is useful in very many applications to introduce the density of
states G(E), which we define to be the fractional number of states be-
+
tween E and E dE. If the energy bands have been specified completely,
the density of states can be determined from the expression
in which is the volume of the unit cell. The integral is taken over a sur-
face of constant energy. I n this section, the implication of the periodicity
and symmetry of a crystal for the density of states will be examined.
The general theory of the density of states has been discussed by Van
Hove26and Phillips27who have considered the bands of lattice vibrational
frequencies. The discussion below follows their work. The reader is
referred to their papers for more detailed discussion and for proofs of the
results quoted. Of particular concern in a discussion of the density of
states is the question of singularities in the function and its derivatives.
This problem arises naturally because of the form of Eq. (7.1). Crystal
symmetry requires that some or all of the components of the gradient
vanish a t various points and along certain lines of symmetry in the
Brillouin zone. We will call a point where VkE = 0 a critical point.
It is not difficult to locate the critical points required by symmetry.
There may exist, however, critical points in addition to those required by
symmetry. To determine the first set we examine the expectation value of
k - P in accord with Section 6, since this determines the linear term in
E(k). If it vanishes, a critical point exists.
Near a critical point, it may happen that the energy possesses a simple
expansion in powers of k:
E(k) = E(ko) + Zi-i*c~i(k - ko)i2. (7.2)
Such a point will be called an analytic critical point. These are the only
26 L. Van Hove, Phys. Rev. 89, 1189 (1953).
2' J. C.Phillips, Phys. Rev. 104, 1263 (1956).
114 JOSEPH CALLAWAY
kinds of critical points considered by Van Hove. If the state #kt belongs
to a degenerate set, the expansion (7.2) is not valid and E(k) is more com-
plicated. Such cases will be called fluted critical points. In addition there
are singular critical points at which one or more components of the QkE’
change sign discontinuously whereas the remaining components vanish.
It is possible to classify the critical points according to the form of the
B(k) surfaces in the vicinity in such a way that the numbers of the various
kinds of critical points are related. In the case in which the simple
analytic behavior of (7.2) occurs four cases are enumerated:
PO:a ~a,2 , aa,all negative (maximum)
PI: a1, a2, negative; positive (saddle point)
P2: (111’ negative, at; aa, positive (saddle point)
Pa:a1, a2,at, all positive (minimum).
Let Pj indicate an analytic critical point of index j: (j = 0, 1,2,3) and let
Nj be the number of such points. Morse has shown that there exist certain
relations among the Nj.” These are:
Phillips has proved that Morse’s relations are also valid for the non-
analytic critical points caused by the existence of degeneracies. Each non-
analytic point can be assigned an index j and a topological weight which
determines the number of times it is counted in entering into the relations
(7.3). These rules are given in Phillips’ paper. The significance of Morse’s
relations is this: the critical points produced by crystal symmetry imply
the existence of others, at a minimum at least as many as are required to
satisfy the relations (7.3). The extra critical points required by the rela-
tions (7.3)may or may not be all those which actually exist.
An interesting and pictorial analysis of the form of the energy surfaces
near a critical point hm been given by R o s e n s t ~ c k .Only
~ ~ analytic
critical points are considered.
The behavior of the function describing the density of states can be
determined in the vicinity of each critical point. The analytic critical
points discussed introduce singularities into the first derivative of the
density of states. More precisely, the density of states varies as d m i
48 M. Morse, “Functional Topology and Abstract Variational Theory,” Memorial
Sciences Mathematiques, Fascicule 92. Gauthier-Villars, Paris, 1938.
40 H. B. Rosenstock, P h p . Rev. 97, 290 (1955); J . Phys. Chem. Solids 2, 44 (1957).
in the vicinity of the critical point. Other types of critical points introduce
different behaviors. Once the various critical points have been located,
the form of the density of states is determined in their neighborhood.
Comparatively simple procedures should suffice to give a reasonable idea
of the remainder of the function. Detailed applications have not yet been
made to electronic energy bands. (See, however, Walker’s treatment of
lattice vibrations in aluminum.a0)Nevertheless, it can hardly be doubted
that these conditions will be important in future studies.
8. NORMAL FORM OF AN ENERGY BAND
It waa pointed out in Section 4 that the uncertainties involved in the
choice of a crystal potential raise the problem of how strongly the results
of a band calculation depend on the choice of potential. It appears from
recent work, principally on the alkali that the shape of an
insolated band of a particular type, such as an s, p , d band, is reasonably
independent of the details of the potential, whereas the relation of the
various bands to each other is more strongly dependent on the potential.
For this reason, it seems useful to define a normal or standard form for a
particular band which is characteristic of a given crystal lattice. The con-
cept of a normal band form may be useful in metals in which a single
band may be of interest for many problems. The usefulness of this ap-
proach may be somewhat less in semiconductors.
By a normal band form we mean the following: At symmetry points
of the Brillouin zone the normal order of levels of a particular type is that
of the corresponding free electron band in an empty lattice. The type of
level is determined by the lowest spherical harmonic in the expansion of
the wave function.*2As an example, consider the levels at the center of
the zone in cubic lattices: I’l is called an s level, r 1 6 a p level, r12and r26r
are d levels, r25 and r2. areflevels, etc. In an “empty” lattice of the body-
centered cubic type, the lowest level would be formed by a plane wave for
which k = 0. This would be of the l’l type. The next levels are those
formed from plane waves of the type (Z?r/a) (1,1,0>.From these, functions
of the type rl, r16,r12,I’w, and I’w can be formed. At the corner point
H, in the same lattice, the lowest levels are those formed from waves
(%/a) (1, 0,0).These waves can be combined to derive functions of the
type Hl, H12, and H16.If the possible levels are examined at these and the
other symmetry points (Pand N) of the zone, and if the levels are classi-
fied according to type using the results of Bell,a2a normal level order can
be constructed. This order is given in Table I for body-centered and face-
30 C. B. Walker, Phys. Rev. 103, 547 (1956).
11 J. Callaway, Phys. Rev. 103, 1219 (1956).
8 ) D. G.Bell, Revs. Modem Phys. 26,311 (1954).
116 JOSEPH CALLAWAY
centered cubic lattices. The Brillouin zones for these lattices are shown
in Figs. 1 and 2.
In both the body-centered and the face-centered lattices, an isolated
S band would be quite simple. The minimum of the band is at the center
TABLEI. NOR- FORM OF ENERGY
BANDS*
I. eband bcc fcc

rl rl
N1 L1
P I XI
HI K1
W1
11. p band bcc fcc

N
11 LV
P4 Xd
Ka
(W z f ,Wa) degenerate in empty lattice
Nd
"'}degenerate in empty lattice xsr
r16 LO
rls
K4
111. dband bcc fcc
HI2 xo
N2 Lo
rrz6p}degeneratein empty lattice r26'
K2
N4 r12
Pa ( X , X s ) degenerate in empty lattice
Hesf W1.
Na
IV. f band rz6 rot

P6 XI.
H6 W2
Nz' XZ'
H2s rzs
rZi Lf
* Levels are listed in order of increasing energy.
of the zone and the maxima occur a t the corners. In the body-centered
lattice, the N1state contains an admixture of d, and the PIan admixture
off functions, so that N1and PImay sometimes be thought of as belong-
ing to the d and f bands, respectively. The band is flat a t PIin spite of the
fact that the group of P does not contain the inversion. In the face-cen-
tered lattice, K 1also contains p functions so that it also belongs to the p
band. L1and X1contain d functions and W1 also mixes f functions.
The form of the p band is quite different from that of the s band. In
the body-centered lattice, we find that the maximum of the band is at
FIO. 1. Brillouin zone for the body-centered cubic lattice. Points and lines of
symmetry are indicated.
FIG.2. Brillouin zone for the face-centered cubic lattice. Points and lines of
symmetry are indicated. This zone also applies to the diamond lattice.
the center of the zone, whereas the minimum occurs on the faces. The
level Pq should be close to the bottom of the band, as should H16.The
situation is similar in the face-centered lattice. The level at the center of
the zone is close to the top of the band; the minimum occurs at the center
118 JOSEPH CALLAWAY
of a hexagonal face. The levels Wi and W 3are degenerate in the empty

lattice. All the p levels also contain f functions. In addition, P I , W Y ,W 3 ,
K3, and K1 contain d functions.
In the d band, the levels at the center of the zone I’26t and I’12 are near
the middle of the band. In the body-centered structure, these levels are
degenerate in the empty lattice, so that they tend to be relatively close
together in the crystal. The separation of the split d levels at the center
of the zone should be considerably smaller than at the corners and faces of
the zone. The maximum of the d band occurs on the face. If N Iis classed
as belonging t o the d band, the minimum will also occur there. The lowest
level which is “really d” is Hlz. The order of the d levels a t the center of
the zone when they are split usually seems to be the reverse of the order
at Hi: namely I’zst is below r12. Consequently there will be accidental
degeneracies on the 100 axis. I n the face-centered structure, the d levels
at the center of the zone are not degenerate in the empty lattice and
should be well separated in real materials, I’ZW being well below r12.The
minimum of the band occurs at the center of a square face or at the corner
W if Wzrand W 3are considered to belong to the d band.
The j band has not been studied as extensively as the others. It is not
so well defined since all the p levels can also belong to the f band, Of the
levels listed in Table I, it is interesting to note that the minimum occurs
at the center of the zone, however, the symmetry of this minimum is
different in the body-centered and face-centered structure.
These ideas are in reasonable agreement with those contained in the
discussions of Wigner and S e W 3although there are differences in detail.
It is difficult to make predictions concerning the relation of the levels
belonging to different band types since this appears to be quite sensitive
to the crystal potential.
9. METHODS OF CALCULATION
Once a crystal potential has been chosen, there remains the problem of
solving the simplified Hartree-Fock equations for enough states to obtain
a reasonable idea of the form of the bands. This is a difficult problem, but
it is one that is becoming tractable because of the development and
widespread availability of electronic computing equipment. No attempt
will be made in this paper to study the methods of calculation in detail.
The attention of the reader is called to ref. 2 and the- citations therein
for such information.
It should be realized, however, that there is no method which is really
practical for a general point in the Brillouin zone. All the methods in
common use involve expansion of the wave function in some set of func-
*a E. Wigner and F. Seitz, Solid State Phy8. 1, 97 (1955).
ELECTRON ENERGlY BANDS IN SOLIDS 119
tions. These expansions must be terminated after a finite, and relatively

small, number of terms. It usually happens that some of the terms at
symmetry points of the zone, or along symmetry axes can be combined so
that the effective size of the expansion is reduced. For instance, if the
OPW (orthogonal plane wave) method is used to determine the state rl
in the body-centered cubic lattice, 135 plane waves can be included in an
expansion involving only eight independent coefficients. It would require
135 independent terms to obtain the same accuracy for a general point.
Continued development of electronic computing equipment may ulti-
mately solve the problem of handling such complex cases. Until then,
calculations will be concerned with points and lines of symmetry. Fortu-
nately, these are of greatest interest, since the maxima and minima of the
bands are most likely to occur there.
Judged by criteria of reliability and widespread use, the principal
methods of calculating energy bands are the cellular method and the
method of orthogonalized plane waves. In the cellular method, the solid
state wave function is expanded in products of radial functions and spheri-
cal harmonics. The orthogonalised plane wave method employs sym-
metriaed combinations of plane waves which have been made orthogonal
to the states of core electrons. The cellular method solves the wave equa-
tion directly. Eigenvalues are determined by requiring that the solutiom
satisfy boundary conditions obtained from Bloch’s theorem on the surface
of the atomic cell. The principal complication of the cellular method lies
in the difsculty of satisfying the boundary conditions exactly. Several
techniques are available, however. The orthogonalised plane wave
method is basically a variational approach. It determines the function of
lowest energy which is orthogonal to a given set of functions. Determina-
tion of the set of core functions required is the most serious problem. A
detailed discussion of the OPW method has been given by WoodruEa4
A third approach, namely the tight binding method, assumes the wave
function in the solid can be obtained aa a linear combination of wave func-
tions for free atoms. Difficulties regarding overlap integrals are so serious
that the results obtained are seldom quantitative. The apparent simplicity
of the method haa led to very wide-spread applications. It is probably at
its best when regarded as an interpolation scheme.
II. The Alkali Metals

10. GENERALDISCUSSION
The alkali metals are such simple physical systems compared to other
metals that the attention given them has been quite out of proportion to
14 T. 0. W o o M , Solid S W Phys. 4,367 (1957).
120 JOSEPH CALLAWAY
their practical importance. They are by far the best understood of all the
metals.
Calculations of energy bands in the alkali metals go back to the early
1930’s. The physical picture proposed by Wigner and Seitz has been ex-
tended to some extent but has not been revised radically. It is well sum-
marized in a recent review.38 Much of the work has been concerned with
the cohesive energy and related properties such as the equilibrium lattice
constant and the compressibility. The essential ideas of Wigner and
Seitz regarding the cohesive energy of the alkalis are as follows. The
cohesive energy is principally the difference of two quantities, the bound-
ary correction and the Fermi energy. The boundary correction is the
difference in energy between the energy of the lowest state of a valence
electron in the solid and in the free atom. It derives its name from the
fact that the boundary condition on the solid state function employed for
the lowest level in the cellular method requires the function to have zero
radial derivative on the atomic sphere. In contrast, the derivative is nega-
tive in the free atom at that distance. Consequently, the kinetic energy
of the electron is less in the solid and the energy is lower. Only two of the
electrons can be in each state, however, and account must be taken of the
distribution of electrons among states of higher energy. The correction is
the Fermi energy, which may be regarded as a repulsive term. It can be
calculated if the density of states is known. The problem of determining
the Fermi energy will be discussed in more detail subsequently. In addi-
tion to these effects, which are the major ones, the Coulomb interaction
of the valence electrons must be also included. It might be thought that
the Coulomb interaction of the valence electrons would yield a very sub-
stantial effect. This apparently is not the case if the correlation energy is
included with the use of Wigner’s formula.36The most recent analysis of
this matter is that of Bohm and Pines, who have investigated the screen-
ing effect of the rest of the electron distribution on the field of any single
electron,6JSwith the use of the collective coordinate method.
*sE.Wigner, Phys. Rev. 46, 1002 (1934); D. Pines’ has discovered an error in the
low density limit of Wigner’s formula. The expression should be E, =
-0.88
rmg*
*ED. Bohm and D. Pines, Phys. Reu. 92, 609 (1953); D. Pines, Phys. Rev. 92, 626
(1955).
The formula for the correlation energy given by Pines (E, = 0.0313 In r. - 0.114)
agrees rather closely with the result of Wigner. There is a significant omission in
Pines’ work480 that a better expression for the correlation energy is E , = 0.0622 In r.
- 0.096. This disagrees very seriously with Wigner’s work for moderately low
densities, r. > 1. However, the expression Gell-Mann and Brueckner is based on an
expansion good only for high densities r. < 1. There is no really adequate treatment
for moderate densities. See, however, E. Wigner, Trans. Furaday SOC.84,678 (1938),
for a discussion of the lowdensity limit. See also J. Hubbard, Proc. Roy. SOC.
(London) OUA, 336 (1957).
The preceding paragraph summarizes the theory of the cohesive

energy in a qualitative fashion. The mathematical theory can be found in
ref. 15. A detailed comparison of theory with experiment will be given
subsequently. It is sufficiently good that one can feel confident of the
basic ideas presented.
OF THE FERMI
11. DETERMINATION ENERGY
The energy must have cubic symmetry (rl)when expressed as a func-
tion of wave number. Since the lattice constants are sufficiently large that
kj < 1 for all the alkalis (k, is the wave number on the Fermi surface), it
is reasonable to expand the energy as follows:
E(k) = Eo + E2k2 + E4(l)k4+ 5E4(2)(k,2ky2+ kw2kz2+ kz2kzz- *k4).
(11.1)
Here EOis the energy of the lowest state of a valence electron, which is
determined by solving the wave equation subject to the boundary condi-
tion d$/dr = 0 for r = rI. The expansion (11.1) breaks down near a
symmetry point at which E(k) is required to have zero slope (except, of
course at k = 0). The quantities Ez and E4c1) can be computed if the actual
atomic cell is approximated by a sphere. Rather than use the perturbation
expansion (6.4) which involves matrix elements, we shall find it is
easier to solve the differential equation of perturbation t h e ~ r y . ~Let
~ . us
~*
write
$k = @*fur
m
uk = knun. (11.2)
n=O
Silverman's results are (to order k2)

u1 = ipl(e)up- T U ~ )
(11.3)
where
He has also given expressions for u3 and u4. The functions f p and fd are the
+
radial parts of the p and d solutions of the equation (- Vz V - Eo)$ = 0.
17 J. Bardeen, J . Chem. Phys. 6,367 (1938).
88 R. A. Silverman, Phys. Rev. 86, 227 (1952).
122 JOSEPH CALLAWAY
The equation satisfied by auo/aE is
(11.4)
Silverman also obtains
(11.5)
and
where
(11.7)
also
(11.8)
and P = rf,.
When (11.7) and (11.8) are used, it is apparent that both E2 and E4
can be obtained if the functions uo,jp, jd, and their derivatives are known
on the boundary of the sphere r = T.. It is not necessary to determine the
functions for all values of T . This result is important in the application of
the quantum defect method. Brooks has given a different formula for El(')
particularly suitable for use in the quantum defect method.gBIt is
where
The Fermi energy is found to be
(11.9)
It is not possible to obtain E42 in this way. The energy surfaces will be
spherical as long as the approximation of replacing the atomic cell by a
*9 H. Brooks, Varenna Lectures, 1957 (unpublished).
ELECTRON ENERGY BANDS .IN SOLIDS 123
sphere is maintained. However, a large value of El(') probably implies

that Ed2 is also substantial.
Brooks has discussed the corrections to the coefficients Eo, E2, and
E4(I)caused by the approximate nature of the boundary conditions in the
spherical approximation. He found that for the alkali metals the correc-
tions to EOand EZare negligible and can be neglected, but that for E4the
corrections may be significant.
12. CRYBTAL POTENTIALS FOR THE ALKALIMETALS
In computing the potential seen by an electron in an alkali metal, the
assumption is commonly made that there is only one electron in each cell.
This is not a result of the Hartree-Fock approximation. This approxima-
tion reduces the density of electrons whose spins are parallel to that of the
one considered producing the Fermi hole, but does not effect the density
of electrons of antiparallel spin in a corresponding manner. It is assumed
on physical grounds that a reduction also occurs in the second density.
It is also assumed that the electron whose wave function is being calcu-
lated is localized in one cell. The potential seen by this electron consists
of its Coulomb and exchange interaction with the charge in that cell (the
ion core field) plus the Coulomb potential produced by the charge in other
cells.*O Since the other cells are electrically neutral and nearly spherical,
the latter contribution is essentially zero. Wigner and Seitz (see ref. 15)
have estimated the errors resulting from the replacement of the poly-
hedron by the sphere of equal volume, the use of free electron functions
to evaluate Coulomb and exchange integrals, 'and similar factors. Such
effects appear to contribute less than 1 kcal/mol to the cohesive energy
in sodium. There are residual uncertainties particularly involving corre-
lation which may amount to as much as 5 kcal/mol. Agreement of a simple
model with experiment within such a factor will be considered satisfactory,
Let ua consider the problem of determining the ion core field. For
lithium and sodium, it is possible to construct empirical potentials which
account rather accurately for the observed spectroscopic energy levels.41*42
These potentials include more than is contained in the Hartree-Fock
equations. For example, part of the core polarization potential is in-
cluded. It is not possible to find adequate empirical potentials for the
heavier alkalis, because the exchange potential varies from state to
40 The use of an ionic potential is, of course, only an approximation. The exchange
and correlation holm are not localized in a particular cell, but follow the electron
around.
41 F. Seitz, Phye. Rev. 47, 400 (1935). An error exists in the printed version of the
potential (for lithium) used by Seitz. The correct form of the potential used is given
by W. Kohn and N. Rostoker, Phys. Rev. 94, 1111 (1954).
42 W. Prokofjew, 2.Physik 68,255 (1929).
124 JOSEPH CALLAWAY
~ t a t e . ' ~Since
. ~ ~ an approach which utilizes the observed spectroscopic
data is more accurate in many respects than one based on a self-consistent
field calculation, there has been considerable interest in the development
of a method for using this information directly. Such a method is the
Quantum Defect Method, frequently abbreviated by the designation
QDM, introduced by Kuhn and Van V l e ~ k and , ~ ~extended later by
Brooks46 and Ham.47 In this method, which is explained in detail in
ref. 47, the spectroscopic information is used almost directly and the
construction of a potential is avoided.
The quantum defect method depends on the circumstance that the ion
core in an atom of an alkali metal is compact and the lattice in the solid is
quite large. The ion core can be assumed to be unaltered in going from
the atom to the solid. Moreover, the field in the outer region of the
atomic cell is just the Coulomb field of the positive ion. The wave function
in this region must be a linear combination of the independent solutions
(regular and irregular functions) of the wave equation for a Coulomb
potential. It turns out that the ratio of the coefficients of the functions is
determined as a function of energy, by a quantity which, for eigenvalues
of the free atom, is closely related to the spectroscopic quantum defect.
This function can be computed for the eigenvalue of the free atom and
must be extrapolated to the energies of interest. Once this function is
obtained, the wave function is determined, apart from normalization, in
the outer part of the atomic cell. This is sufficient to determine both
boundary connection and the Fermi energy, as was shown in Section 11.
This approach is extremely powerful. It includes the exchange inter-
action, and portions of the correlation interaction between the valence
and core electrons, as well as the average electrostatic interaction in the
interior. Relativistic effects are included for s states and with a slight
extension may also be included for other states. It does not include effects
which alter the field at large r, such as the polarization, which varies as
l/r4 for large r. It should be mentioned, however, that the empirical
potentials usually do not contain such large T effects. It appears to be
possible to correct the quantum defect method to include the polarization.
48 It is probable that one could h d , however, a set of empirical potentials, one for
each angular momentum.
44 A simplified version of the empirical field approach was devised by H. Hellmann
and W. Kassatotschkin, J . Chem.Phys. 4,324(1936);ActaPhysiwchim. 6,23 (1936),
and applied with good success to the calculation of the cohesive energietl of Ns, K,
Rb, and Cs.
46T. S. Kuhn and J. H. Van Vleck, Phys. Rev. 79,382 (1950).
46 H.Brooks, Phys. Rev. 91, 1027 (19531,and unpublished work.
47 F. 6. Ham, SoZid State Phys. 1, 127 (1955).
'
The principal difEculty encountered by the quantum defect method

probably is the practical one of extrapolating the crucial function of
energy [Ham’s 7(E)]from the spectroscopic eigenvalues to the range of
energies of interest in the solid. There is no completely satisfactory method
of doing this. Inclusion of approximate core eigenvalues, as proposed by
Ham4’ does not appear to be of much help. It remains to be seen how
much uncertainty is introduced into the method by the difficulties of
extrapolation. Possibly such uncertainties also are implicit in the case of
empirical potentials.
13. COREPOLARIZATION
An alternative to the use of an empirical potential or the quantum
defect method is to use a potential obtained from a self-consistent field.
Even when the ordinary potential is supplemented by an explicit exchange
interaction between valence and core electrons, the eigenvalues obtained
are usually higher than those obtained by the other methods. This prob-
ably is principally the result of the neglect of the correlation between
valence and core electrons. It is possible, however, to include some of the
effect of this correlation in the form of an ordinary potential which may
be added to a self-consistent field calculation.
The polarization of the ionic core by the valence electron is one form
of correlation. In &st approximation, the ion is spherically symmetric so
that the electric field external to it is characterized by the potential
energy -ee/r. The external electron distorts the core, however, and
induces in it a dipole moment proportional to the polarizability of the
ion. The field of the distorted core then reacts back upon the valence
electron, decreasing its potential energy by an amount proportional t o
e2/2r4at large r. Higher electropole moments are also induced. If the T-4
dependence of the polarization potential persisted to T = 0, an infinite
contribution to the energy would result. Actually it does not, and a more
elaborate treatment is req~ired.~8
Such a treatment of polarization has been given using the Hartree-
Fock wave functions for the core electrons.4gUnder the influence of the
field of the valence electron, the one-electron wave functions of the
core electrons depend parametrically on the coordinates of the valence
electron. Consequently the energy of the core electrons is also a function
of the position of the valence electron. This coordinate-dependent energy
40 Some attempts to determine approximate polarization potentials are discussed by
D. R. Hartree, “The Calculation of Atomic Structures,” p. 162. Wiley, New York,
1957.
4s J. Callaway, Phys. Rev. 106,868 (1957).
126 JOSEPH CALLAWAY
then serves as a potential energy function for the valence electrons. After
a number of approximations a polarization potential is derived :
4Zi
v,(r>= Tt. ui(o)(rl)rlcos e ui(l)(rl,ro) drl. (13.1)
The function ui(*) is the unperturbed core function for the state i, whereas
UP)is the perturbed function which was obtained from the work-of
Sterr~heimer.~~ Explicit polarization potentials were obtained for lithium,
sodium, and potassium.4sThe potentials probably tend to overestimate
the effect since Sternheimer’spolarisabilities appear to be somewhat large.
In the case of potassium, for example, the calculated polarization poten-
tial lowers the 4s energy level below the experimentally observed value.
The polarization potential calculated according to (13.1) would make
a very substantial contribution to the cohesive energies of potassium,
rubidium, and cesium. This contribution would spoil the rather good
agreement between theoretical and experimental values of the cohesive
energies for these elements obtained by both the quantum defect method
and the self-consistent field approach, when polarization is neglected.
Brooks has suggested that the polarization potential is reduced in the
solid compared to the free atom.s1 The polarization interaction may be
screened by the valence electron distribution so that it is nearly zero
on the boundary of the atomic cell. The screening of the polarization
potential in the solid is one of the most important problems remaining in
the study of the cohesive energies of the alkali metals. (See also Section
17.)
14. RELATIVISTIC EFFECTS

It is pos&ible to formulate the theory of the cohesive energies of the
alkali metals on the basis of the relativistic self-consistent field equation.62
This equation, developed by S w i r l e ~considers
,~~ the relativistic motiqa of
one electron in the average electrostatic field of the other electrons, but
does not consider the relativistic interaction of the electrons. The source
of the relativistic effects is the rapid motion of the electron in the strong
attractive field near a nucleus. It is known that such effects are not
negligible in solids. For example, there is a substantial splitting of the
levels at the top of the valence band in germanium as a result of the spin
orbit coupling.
60 R. M. Sternheimer,Phys. Rev. 96,951 (1954).
61 H. Brooks, Private communication.
6 1 J. Callaway, R. D. Woods, and V. Sirounian, Phys. Rev. 107,934 (1967).
6) B. Swirles, Proc. Roy. SOC.(London) A162, 625 (1935).
ELECTRON ENERGY BANDS IN SOLID8 127
Unfortunately, existing self-consistent fields for free atoms usually do

not include reIativistic effects. The corrections arising from the relativ-
istic motion of an electron in the nonrelativistic self-consistent potential
can be calculated by perturbation theory. These are reasonably sub-
stantial for cesium, being at leaat 10% of the cohesive energy, and tend to
increase the binding. There is something else to be considered, hotvever.
The relativistic effects lead to increases in the binding of the core electrons
relative to the energies obtained in a nonrelativistic calculation, so that
the wave functions are drawn further in toward the nucleus. Thus the
screening of the nucleus by the core electrons is more effective. This in
turn, reduces the depth of the potential seen by a valence electron and so
tends to cancel the extra binding. Both effects can be included in a calcu-
lation usin@; a quantum defect method.
The boundary correction is obtained in the same way as in the
ordinary theory. The Dirac equation or, more properly, the relativistic
self-consistent field equation is to be solved, subject to the condition that
the large component have a zero normal derivative on the atomic sphere.
The calculation of the effective mam can be made with the method of
Silverman.**Bloch’s functions #k = e*%k are used. The function tkk is
expanded in powera of k. The first- and second-order perturbed functions
u;satisfy the relations:
(-ca - p + B ~ c *+ V - Eo)ul = h a kuo
(-ca * p + 0 ~ +~V 9- E&z = h a * kul+ Ezuo. (14.1)
The result of the calculation is that
(14.2)
where
The functionsfa*, fpr, and f& are solutions of the Dirac equation for states
s and p states of j = 8 and j = # (all have mj = 4). The prime indicates
differentiation with respect to r. This equation is the relativistic extension
of (11.5). A relativistic expression for E P can also be obtained.64
A quantum defect calculation has been carried out for cesium using
(14.2).62 The boundary correction given by the ordinary QDM contains
all important relativistic effects. It was necessary to obtain quantum
defects separately for p states of j = 8 and j = 3. There was considerable
uncertainty in extrapolating the defects. There are indications, however,
64 F.S. Ham, Private communication.
128 JOSEPH CALLAWAY
that the net relativistic effect is small, of the order of 1% of the cohesive
energy. This implies that there is almost exact cancellation between the
extra binding and the stronger screening. The relativistic effects doubtless
would be more important in a calculation of the magnitude of the wave
function at the nucleus, which is involved in the theory of the Knight
shift.
15. LITHIUM
There have been many studies of energy levels in lithium.a7-39~41~60~6s-e3
Most of the early work is summarized in the book of Seitz,16and will not
be discussed in detail here. It is convenient to consider first the calcula-
tions pertaining to the lowest band.67~68~60~e2~*a
These calculations employ
the empirical potential of S e i t ~ . ~The
' results obtained for the band
parameters of Section 11 are presented in Table I1 (for the observed
TABLE11. BANDPARAMETERS
FOB LITHIUM
Silverman and Kohn and Brooks Brown and

Kohn, Silverman &stoker (r, = 3.20) Glaaser and Callaway h m h a n s l
Eo -0.6832 -0.6832 -0.6865 -0.6863 -0.6827

Es 0.727 0.723 0.7305 0.755
El(" -0.031 +0.039 -0.0303
El(') -0.033
lattice constant ra = 3.21 except a noted). The cohesive energy of

lithium obtained by Silverman and KohnS7and Silverman is given in
Table 111. The quantities EB and EI are given. Es is the sum of the
boundary correction and the Fermi energy.
EB= Eo - Ea + 2.21E2/ra2+ 5.81E4/ra4. (15.1)
Here Ea is the energy of the valence electron in the lowest state of the free
atom; in this case E,, = -0.3906 ry.
55 J . Millman, Phys. Rev. 47, 286 (1935).
56 C. Herring, Phys. Rev. 69, 598 (A) (1939).
67 R. A. Silverman and W. Kohn, Phys. Rev. 80,912 (1950); 83, 283 (1951).
68 C. Herring, Phys. Rev. 83, 282 (1951).
60 R. H. Parmenter, Phys. Rev. 86, 552 (1952).
60 W. Kohn and N. Rostoker, Phys. Rev. 94, 1111 (1954).
6 1 B. Schiff, Proc. Phys. Soc. (London) A67, 2 (1954).
6) M. L. Glwer and J. Callaway,Phys. Rev. 109, 1541 (1958).
68 E. Brown and J. A. Krumhansl, Phys. Rev. 109,30 (1958).

EX is the energy of electron interaction calculated with Wigner’s

formula for the correlation energy.
(15.2)
The cohesive energy is -E, = EB + EX.

TABLE111. COHESIVEENEEQY
OF LITHIUM
EB = -0.1384 (ry) = -43.2 kcal/mole

EI = +0.0085 (ry) =i 2.7 kc4/mole
E, = 0.1299 (ry) = 40.6 kcd/mole (theoretical)
EC = 36.5 kcal/mole (experimental)
The QDM calculation of BrooksBQ leads to a value of -0.1399 ry for EB

and thus to a cohesive energy of 41.1 kcal/mole. The agreement between
theory and experiment, while reasonably satisfactory, is not remarkable.
The principal uncertainties in the results quoted probably lie in the elec-
tron interaction energy (perhaps as much as 5 kcal/mole), and in the
polarimtion correction.
I n a previow calculation, based on an earlier form of the quantum
defect method, Brooks found the lattice constant of lithium to be
3.40 A,46.47 which is to be compared with the experimental value of
3.43 A. He also estimated the theoretical pressure corresponding to the
compression which is experimentally observed at 10,OOO atmospheres and
obtained a value of 10,500 atmospheres. These results are less sensitive to
uncertainties in the correlation energy than is the cohesive energy.
It is interesting to note that lithium is the only alkali metal for which
the effective mass at the bottom of the band found by calculation is
greater than the free electron mass. This can be interpreted with the use
of the formulas of perturbation theory (6.4) to be a consequence of the
absence of a p state in the core.
Herring attempted an orthogonalized plane wave (OPW) calculation
of energy levels in lithium56but the results were not published in any
detail. Parmenter has also made an OPW calculation of energy bands in
lithium.sQHis potential was adapted from a self-consistent field calculation
and exchange was included by Slater’s averaging process. His potential is
probably not as good a representation of the state of affairs as Seitz’s
potential is. There are, in addition, several unfortunate features in regard
to the use of the OPW method in Parmenter’s calculation. In the first
place Parmenter represented the 1 s core function as an exponential with
a variationally determined constant. This is likely to be inadequate be-
cause it does not represent properly the tail of the wave function, which
130 JOSEPH CALLAWAY
makes a significant contribution to the orthogonality coefficients. Also,

it is not evident that Parmenter has included enough plane waves to
insure convergence of the expansions. Parmenter believes that a spurious
term in his potential renders it impossible for him to determine Eo, how-
ever, he believes that the value for Ez, 0.808, is significant.
Schiff has made a calculation of energy levels in lithium using the
cellular method. Unfortunately, the correct Seitz potential was not
available to him. He has determined a semiempirical potential according
to the manner of Prokofjew, but his potential does not bind as tightly as
that of Seitz and is probably somewhat less accurate. Energy values were
calculated for the states rl, NI', NI, HI, H12, Hla.
Wainwright and Parzen have attempted a calculation of energy levels
in lithium using a variational method based on Wannier f u n ~ t i o n sThe
.~~
(corrected) Seitz potential was employed. The results do not compare
well with those derived by the cellular or the OPW method using this
potential. The trouble appears to be in the determination of the 1sfunc-
tion, which has to be found by numerical integration both in their method
and in the OPW procedure. They obtained an energy EIS= -5.35 ry for
this function whereas Glwer and Callaway6zfound EIS = -3.765.
Brown and Krumhans16*have recently calculated energy levels in the
lowest band of lithium by a variational procedure closely related to the
OPW method. The Seitz potential, in corrected form, was employed.
Energies were determined for states at the center of the zone and with
wave vectors along the 100 and 111 axes. The results for levels below the
Fermi surface are in fairly good agreement with those of Kohn and
Rostoker,60and the energy of P I at the zone corner is close to that deter-
mined by Glasser and Callaway.6z
Glasser and Callaway have recently completed an OPW calculation
for lithium."*The Seitz potential was used. A 1s core function was deter-
mined by numerical integration for this potential as is required by the
OPW method. The principal object was to determine the positions of
higher states at the symmetry points of the Brillouin zone. The energy of
the lowest state I'l is in good agreement with the results of the cellular
method. Calculations were made for 24 irreducible representations at the
four symmetry points I', H , P, and N. The convergence of the OPW
method was very good for s-like states and reasonable for p and d states.
The results are given in Table IV and shown graphically in Fig. 3. The
order of levels in the isolated 8, p , and d bands is completely in accord
with the normal level order for the body centered cubic lattice.
Callaway and Glasser have recently shown that inclusion of the
04 T. Wainwright and G.Parzen, Phys. Rev. 92, 1129 (1963).
potential of the valence electron distribution cannot appreciably affect

the energies of the levels in lithium.'" The crystal potential is required
by symmetry, however, to have a vanishing normal derivative on the
surface of the atomic polyhedron. The Seitz potential does not have this
TABLE
IV. ENERGY
LEVELSIN TEE ALKALIMETALS(OPW)METHOD
Stab m
' Lithium sodium Potassium Cesium
~~ ~ ~~
dike
rl 0.0 -0.6863 -0.5974 -0.4304 -0.5286
N1 0.5 -0.176 -0.263 -0.224 -0.285
P1 0.75 +O .330 -0.041 +O .054 -0.118
HI 1 +O .571 +O .193 +O. 265 +O. 144
p-like
N1. 0.5 -0.4042 -0.316 -0.190 -0.342
PI 0.75 -0.1887 -0.162 -0.126 -0.259
HI5 1 -0.0920 -0.015 +O .062 -0.173
Nt 1.5 +O .174 +O .301 +O. 176 -0.009
N1, 1.5 +O .475 +0.310 +O .356 +O .069
rls 2 +O .617 +o .632 +O .699 +O .269
d-like
1 +O .227 -0.132 -0.208
1.5 +O .524 +O .055 -0.167
2 +O .854 +o .220 -0.116
2 +1.146 +O .264 +O .042
2.5 + l.
148 +O. 436 +o .099
2.75 +1.60 +O .486 +O .098
3 +1.83 +O. 537 +O. 130
3.5 +2.21 +O .694 +o. 242
"he quantity m*,*
)k:(
= where k is the wave vector of the lowest OPW in the
expansion for the particult& state.
property, as is also the case for the potentials used in the calculations of
energy levels in potassium and cesium. This probably does not affect r,
signxcantly, but may dter the other levels by f0.05 rydbergs.
It is to be noticed that the lowest band is bounded by states of p-like
character, namely HIS,PI,and NI',in agreement with the results of
~ ~ is no evidence to support Mott's conjecture that states on
S C M .There
the boundaries of the first Brillouin zone are of S character." This p r e
640 J. Callaway and M. L. Glaaser, to be published.
6s N. F. Mott, Phil. Mag. [7] 44, 187 (1953).
132 JOSEPH CALLAWAY
+I.!
+I.(
n
cn
2 +.!
(3
m
*a
P
CI
5
a
W
W
z t
,I
.*
-1.c
FIG.3. Energy level diagram for lithium according to Glaaser and Callaway.6*
.Lev& at four symmetry points up to 1.5 rydbergs are shown.
posal waa introduced in an attempt to explain the soft x-ray emission

spectrum of lithium.66The spectrum shows a falling off in intensity before
the Fermi surface is reached. Since transitions are observed from the con-
66 D. E. Bedo and D. H. Tomboulian, Phys. Rev. 109, 35 (1958); J. Callaway, Bull.
Am. Phys. Soc. [2] 3, 29 (1958).
duction band to the 1s level, it was supposed that S-like states were
prominent on the Fermi surface.
16. SODIUM
Calculations of energy levels in sodium have been made by many
The early papers of Wigner and Seitz listed
workers.z8~8s~41~4~41~01-~1Q
here0?@ form the foundation of the theory of cohesive energy. The
results are summarized adequately in Seitz’s bookl5 and will not be dis-
cussed further. The original band calculation by Slater08suffers, as do
many similar calculations, from insufficient accuracy in the application
of the cellular method boundary condition^.'^ Von der Lage and Bethe
presented a method whereby much of the diEculty could be overcome.
The problem cannot be said to be solved completely however.
The parameters pertaining to the bottom of the band are presented
in Table V. The observed lattice spacing corresponds to T. = 3.94 at
0°K. The value of E P given in Table V was determined by Callaway at
a somewhat larger lattice spacing, T, = 4.07.
V. BANDP m m ~ FOB
TABLE s SODIUM
Bardeena Brooksb
(r. = 3.96) (r. = 4.0)
EO -0.610 -0.6011
E2 1.069 1.022
E p -0.051 -0.0096
Q J. Bardeen, J . Chem. Phys. 6, 367 (1938).

b H. Brooks, F’rivate communication. The valuea attributed to Brooks have been
found by quadratic interpolation in the published results. Equation (15.2) was used
to compute EI.
The cohesive energy is given in Table VI according to the band pa-

rameters of Bardeen.
The QDM calculations of Brooksaalead to a value of -0.0824 for EB
and to a cohesiveenergyof 26.8kcal/mole for T. = 4.0. The agreement with
experiment is quite respectable. The theoretical uncertainties, particu-
larly those concerning the correlation energy, are sizeable. In this respect,
67 E. Wigner and F. Seitz, Phys. Rev. 45,804 (1933).
68 J. C. Slater, Phys. Rev. 46, 794 (1934).
6oE. Wigner and F. Seitz, Phys. Rev. 46,509 (1934).
70 F. C. Von der Lage and H. A. Bethe, Phys. Rev. 71, 612 (1947).
71 D. J. Howarth and H. Jones, Proc. Phys. SOC.(London)A66, 355 (1952)
noJ. Callaway, Phys. Rev. to be published.
7) W. Shockley, Phys. Rev. 51, 129 (1937).
134 JOSEPH CALLAWAY
it is curious that the net effect of the Coulomb interaction is an increase

in the binding energy.
The equilibrium lattice constant obtained by Brooks is 4.26 A which
is to be compared with the experimental value of 4.26 A. The theoretical
pressure corresponding to the compression which is experimentally
observed at 10,OOO atmospheres is 9OOO atmospheres.
Uwdin haa calculated the cohesive energy of sodium by a method
quite Merent from those ordinarily used for metals.7aHis method is an
adoption of. the tight binding approximation and considers overlap
integrals for quite distant neighbors. He obtained values for the cohesive
TABLEVI. Comsm ENEEGY

OF SODIUM
EB = -0.0814 (ry) = -25.5 kcal/mole

EI = -0.0032 (ry) = - 1.0 kcal/mole
E, = +0.0846 (ry) = 26.5 kcal/mole
EO = 26.0 kcal/mole (experimental)
energy and lattice spacing (24.7 kcal/mole and a lattice constant of

3.67 A aa compared with 4.22 A), but did not include any correction for
the correlation energy. This calculation haa been criticized by Raime~7~
on the ground that his I'l wave function is a poor approximation to the
solution of the Hartree-Fock equation and is not orthogonal to the core
states. For this reason, the agreement with experiment probably is
accidental.
Calculations of higher energy levels in sodium are not as complete
as for lithium. The cellular method has been used to study a few of the
low-lying levels at r, H , P, and N.28*47J0s71 The calculations of Von der
Lage and Bethe, Bowers, and Howarth and Jones were based on the
Prokofjew potential. The results are presented in Fig. 4. In the case of
conflict, the results of Howarth and Jones are given. It may be noted that
the bands are not as wide as in lithium. In particular the d levels have
been lowered with respect to 8 and p states. The lowest band appears
to be quite accurately parabolic, with an effective mass ratio close to
unity. The lowest level at the point N , which is the symmetry point
nearest the Fermi surface, is N 1 which is s-like. Ham,47however, has
found in his QDM calculation, using a slightly different lattice constant,
that N1' is lower than N1. At any rate, the states N1 and N1'are much
closer than in lithium. Not enough levels have been computed to make a
good comparison with the normal order of levels.
'8 P.0.Liiwdin, J . Chm. Phys. 19, 1570, 1579 (1951); Advances in Phys. 6, 1 (1956).
74 S. Raimea, Proc. Phys. Soc. (Londrm)A67, 52 (1954).
The relative closeness of N Iand Nr' suggests that the proportion of
s-Ue states on the Fermi surface is greater in sodium than in lithium.
This is supported by magnetic resonance measurements see Section 20)76
and is also consistent with the soft x-ray emission data. 1.00
+ .6
+.5
+.4
+.3
+.2
+.I "HI
Q --H 12
-.I c,. E.
J'HIII
-.2
-.3
-.4
-5
-.6
E r H P N
FIQ.4. Energy level diagram for eodium according to r d t e of Von der Lsge and
Bethe70 and Howarth and In ewe of disagreement, the rerJulta of the latter
authom am shown.
The simplified empirical field approach to the determination of the
crystal potential originated by Hellmann and Kassatots~hkin4~ has been
applied to the calculation of energy levels of predominately s and p
symmetries in sodium.71aThe potential in one cell is written as
(16.1)
The constants A and B were adjusted so that agreement is obtained with

16 H. Jones and B. SchitT, PTOC.
Phys. SW. (London)A67.217 (1964).
136 JOSEPH CALLAWAY
the lowest s and p levels of the valence electron in the free atom. The
values obtained were A = 24.578 and 13 = 2.101. The second term in
(16.1) includes the effect of orthogonality of the valence electron wave
function on those of the core electrons as a repulsive potential, so that the
lowest bound state in this potential pertains to the valence electron. A
plane wave method was applied to calculate energy levels in this potential.
The results are included in Table IV. They are in good, though not exact,
agreement with those of Ham.
17. POTASSIUM
There have been several calculations of energy levels in potas-
sium.81~46~46J6J7In the first calculation, Gorin78 found it impossible to
construct an empirical potential which would account for all the spectro-
scopic data. His calculation of the cohesive energy was based on a self-
consistent field. The results are summarized and discussed in ref. 15.
Sufice it to say here that he did not obtain reasonable agreement with
experiment, but found a cohesive energy which is much too small and a
lattice constant much too large. Gorin also had to make a rather arbitrary
assumption of increased correlation energy in the solid as compared with
the free atom. The failure of Gorin’s work probably stimulated the devel-
opment of the quantum defect method.
It has been shown, however, that inclusion of an exchange interaction
between valence and core electrons makes it possible to obtain a reason-
able value for the cohesive energy.T7 The parameters pertaining to the
bottom of the band are listed in Table VII.
TABLEVII. BANDPARAMETERS
FOR POTASSIUM
Callawaya Brooksb
(7‘ 4.84) (r. = 4.86)
Eo -0.4525 -0.4876
E2 1.168 1.149
Ed(’) -0.4 -0.3
~ ~~~~~~~~~
a J. Callaway, Phys. Rev. lOS, 1219 (1956);S. Berman, J. Callaway, and R. Woods,
Phys. Rev. 101, 1467 (1956). A numerical error was discovered in the calculation of
El reported in ref. 36. The correct value is given here.
b H. Brooks, Phys. Rat. 91, 1027 (1953);unpublished work; private communication.
The cohesive energy of potassium can be computed on the basis of the

foregoing parameters. The results are given in Table VIII (for r8 = 4.84).
76 E. Gorin, Phys. 2.sourjetunia 9,328 (1936).
77 5. Berman, J. Callaway, and R. D.Woods,Phys. Rev. 101, 1467 (1956).

Since an empirical potential is not used for potassium, a polarization cor-
rection is important in a calculation based on the use of a self-consistent
field. The correction computed in ref. 37 amounts to 8.7 kcal/mole and
spoils the agreement between theory and experiment obtained in its
absence, however, the numerical value obtained in that paper is open to
question for two reasons. The first of these is that Sternheimer’s polar-
isabilities probably are too large. The second is the likelihood of screening
of the polarization field by the valence electron sea. These corrections
cannot be calculated on the basis of any theory. A crude estimate would
ENERGY
TABLEVIII. COHESIVE OF POTASSIUM
Ee = - 0 . 0 5 5 ~ -
= 17.2 kcal/mole
Er = -0.011 ry -
= 3.4 kcal/moIe
E, = +0.066 ry = 20.6 kcal/mole (simple model)
Correction (polarization) = 2.6 kcal/mole
E. (including polarization) = 23.2 kcal/mole
E
C = 22.6 kcal/mole (experimental)
be to scale the polarization potential on the basis of the values of Van

Vleck,’S and to take account of the screening by adding an energy equal
to the magnitude of the polarization potential on the boundary of the
sphere.s1 When this is done, the polarization connection is reduced to
2.6 kcal/mole. This result gives a very reasonable cohesive e11ergy.7~
Brooks’ values for the band parameters quoted in Table VII already
include a polarization correction, but not the constant factor added to
account for the screening. The cohesive energy obtained in this way
amounts to 20.4 kcal/mole. An earlier calculation of Brooks lead to a
maximum cohesive energy of 22.2 kcal/mole for a lattice constant of
5.16 A as compared to the experimental value of 5.20 A.46
Callaway investigated higher energy levels in potassium in an OPW
calculation.81 Crystal potentials including exchange were calculated
separately for s-, p-, and d-like states with the use of approximate wave
functions. Core states were not determined for s and p states in this par-
ticular potential, however, the solutions of Hartree’s self-consistent field
with exchanges0 for the free K+ ion were used. Since exchange was
78 J. H. Van Weck, “The Theory of Electric and Magnetic Susceptibilities.” Oxford,
1932.
’9 Scaling the polarization potential reduces the correction from 8.7 to 5.7 kcal/mole.
The polarization potential on the sphere surface amounts to 3.1 kcal/mole. The net
effect is then 2.6 kcal/mole.
(0 D. R. Hartree and W. Hartree, Proc. Roy. Soc. (London) A166, 450 (1936).
138 JOSEPH CALLAWAY
included in this calculation, thk error may not be too serious. Energy
values were computed for twenty-f our irreducible representations at four
symmetry points of the Brillouin zone: r, H,P, and N. Although the
convergence of the OPW method was not as good as that obtained in
lithium, most levels are probably convergent to 0.04ry. This accuracy is
H N
HI--
H15--
p4 - Nz*--
N4-
-rNz
--t44'
HP-- N3--
p5-
NI --
"26'-- Nt--
p3-
N4--
N3'--
Hy- NI--
N4*--
"IS-' PI- N2--
H12-- p4 -
N I ' 1 S
NI
H P N
FIG.5. Energy level d h g ~ r t mfor potassium according to Callsway.*l Levels at
four symmetry points up to 1 rydberg are shown.
sufficient to answer most questions regarding the order of levels. Some of

the results are shown in Fig. 5 and in Table IV.
Comparison of the results for sodium and lithium reveals a marked
lowering of the d levels in potassium relative to the s and p levels, This
would be expected from the position of potassium in the periodic table.
The separated bands conform to the normal order of levels for the body-
centered cubic lattice.
Experimental information pertaining to the effective masses of elec-
trons on the Fermi surface in potassium and in other alkali metals comes
from optical measurements by Ives and Briggs.81 The alkali metals be-
come transparent in the near ultraviolet. This phenomena can be ex-
plained simply on the basis of a free electron theory and can be used to
determine an effective mass on the Fermi surface. More precisely, the
optical effective mass is (if interband transitions can be neglected)B2
l/mo = - VkEdsp =
3(2~)~N
~ 1 Vk2Ed31C. (17.1)
The surface integral in (17.1)extends over the Fermi surface, the vol-
ume integral over the occupied part of the Brillouin zone. If the bands
are spherical, the result is the ordinary effective mass on the Fermi sur-
face. Cohen has made a least squares fit to the dielectric susceptibility
determined from the index of refraction and absorption measurements
of Ives and Briggs with a function of the form A - B/u2 where w is the
circular frequency of the light.82The optical effective mass can easily be
determined from the value of B, and the result for A can be related
to the core polarizability. Cohen finds the following values: sodium,
mo/m = 1.01 f 0.02; potassium, 1.08 f 0.02; rubidium, 1.08 f 0.03;
and cesium, 1.02 f 0.02.Since the effective masses a t the bottom of the
band ( ~ / E sare
) less than unity for potassium, rubidium, and cesium
according to the band calculations, the results indicate significant nega-
tive Ed terms in these elements. Detailed calculations of mo would require
evaluation of the integral (17.1).
The soft x-ray emission spectrum of potassium has been observed.8a
Transitions between the conduction band and the 3p levels were
studied. The shape of the spectrum is consistent with a dependence of the
density on a factor EI which is to be expected from s-p transitions. The
band width is about 1.9ev, which is somewhat smaller than the value of
2.4 ev predicted from the data of Table VIII.
The relatively large value of Edindicates that the electrons in potas-
sium should not be considered as free. It also suggests that there may be
significant departures of the Fermi surface from spherical symmetry.
81 H.E.Ives and H.B. Briggs, J . Opt. Soc. Am. 26, 238 (1936): K;27, 181 (1937):
Na; 27, 395 (1937): Rb and Cs.
** M.H. Cohen, Phil. Mag. [S]8, 762 (1958).
8*R. H. Kingaton, Phys. Rev. 84,944 (1951).
140 JOSEPH CALLAWAY
18. RU~IDIUM
AND CESIUM
The heavier alkali metals have not been studied as extensively as

the lighter ones. Less work has been done on r ~ b i d i ~ m ~than ~ .on~ ~ + 8 ~ ~
cesium.46.46.84-66
The early work of Gombas,s4 who considered sodium, potassium,
rubidium, and cesium, was based on a method in which perturbation
theory was applied to free electron wave functions. He used a semi-
empirical potential. In the lowest order, he replaced the actual potential
in he exterior of the atomic cell by a constant, its average value. The
TABLE FOR RB AND Cs

IX. BANDPARAMETERS
Rubidium Cesium
Callaway and Callaway and

Brooks Morgan Sternheimer Haase Brooks
(r. = 5.21) (rr == 5.21) (re = 5.64) (r, = 5.735) (r, = 5.64)
Eo = -0.462 -0.4442 -0.4258 -0.4156 -0.4274

Ep 1.10 1.181 1.336 1.393 1.197
El(') i -1.28 -3.64
difference between the potential and its average was treated as a per-
turbation. This procedure may be reasonably valid since the potential
varies slowly over most of the volume of the cell. The energy of the ground
state so obtained is in reasonable agreement with other determinations.
Unfortunately, incorrect boundary conditions were used for the state
believed to lie a t the top of the band.
Callaway and Morgan calculated the cohesive energy of rubidium
using a potential obtained from a self-consistent field for Rb+, supple-
mented by an exchange potential.Sh The exchange potential was con-
structed from the Hartree-Fock equations using a trial wave function.
The values of the band parameters and the cohesive energy are given in
Tables IX and X respectively.
The calculation of S t e r ~ ~ h e i r n was
e r ~ ~designed to test the hypothesis
that an observed discontinuity in the compressibility of cesium at high
pressures is the result of a crossing of 6s and 5d bands. He tried to locate
the positions of these bands as a function of interatomic distance. A
O4 P. Gombh, Z. Ph.ysik llS, 150 (1939).
J. Callaway and D. F. Morgan, Phgs. Rev., to be published.
*6 R. M. Sternheimer, Phys. Rev. 78, 235 (1950).
J. Callaway and E. L. Haase, Phys. Rev. 108, 217 (1957).
potential based on a Hartree field was used; however, exchange was
included and the result was adjusted in order t o agree with the energy
of the lowest state of a valence electron in the free atom. Unfortunately,
Sternheimer used inappropriate boundary conditions for the d band,
which probably has a shape quite different from the simple parabolic
form he predicted. This error makes much of his calculation invalid.
However, his results for the s band are reasonably good in the vicinity
of the observed lattice constant.
Callaway and Haasess made a calculation of the energy bands in
cesium. The bottom of the s band was studied by the cellular method and
the OPW method was applied to the higher states. The parameters per-
taining to the bottom of the band in Rb and Cs are presented in Table IX.
The cohesive energy computed from these data is given below in
Table X. The values attributed to Brooks were found by interpolation
TABLEX. COHESIVEENERGIES
OF RUBIDIUM
A N D CESIUM
Rb Rb (Callaway and Morgan)
EB = -0.0651 = 20.4 kcal/mole EB = -0.053 ry = 16.6 kcal/mole

EI = -0.0132 = 4.1 kcal/mole EI = -0.013 ry = 4.1 kcal/mole
E, = +0.0781 = 24.5 kcal/mole E, = -0.066 ry = 20.7 kcal/mole
Ee (exp.1 = 18.9
CB (Brooks) Cs (Callaway and Haase)
EB = -0.0580 ry = 18.1 kcal/mole EB = -0.0556 ry = 17.4 kcal/mole

El = -0.0152 = 4.8 kcal/mole EI = -0.0156 ry = 4.9 kcal/mole
E , = -0.0721 = 22.9 kcal/mole E, = -0.071 ry = 22.3 kcal/mole
Ei (exp.) = 19.7
between the published values. Polarization effects are not included in

these results. For rubidium, Brooks obtained a lattice constant of 5.45 A,
which can be compared with the experimental value 5.56 A. For cesium,
he found the lattice constant to be 5.93 A. The experimental value is
5.92 A. The pressure corresponding to the observed compression a t
10,000 atmos was found to be 7200 and 13,000 atmos in rubidium and
cesium, respectively.
The crystal potential used in the calculation of Callaway and Haase
was adopted from that of Sternheimer and reproduces the experimental
value for the lowest energy state of the valence electron in the free atom
approximately. This potential was used for all states. An error which may
be considerable in an atom as heavy as cesium is introduced. Core states
were found by numerical integration using this potential.
142 JOSEPH CALLAWAY
The OPW method appears to converge quite satisfactorily. There is

an uncertainty of the order of 0.05 rydberg in regard to the position
of the levels. A level diagram is shown in Fig. 6. Some energy values are
given in Table IV. The calculated bands in cesium exhibit two striking
+.7- -
+.8- -
+.3- -
*0
CI
c
Y
m
-=
a
I-
+.I--
*0
B
"t -.\--
-.3- -
-.6- -
r n P N
FIG.6. Energy level diagram for cesium according to Callaway and Haase.86
Levels at four symmetry points up to 0.75 rydberg are shown.
features. First, there is a general tendency for the bands in cesium to be

narrower than in the other alkali metals. Something of this nature would
be expected because of the larger lattice constant. It is interesting to note
that, in spite of this tendency, the separation of the split d bands at the
center of the zone is larger than in potassium. Second, the p levels tend
to be rather low compared to s levels. This is probably sensitive to details
of the potential, but is reasonably consistent with a substantial negative

value of EJ.~'
The higher levels conform reasonably well to the normal order of
levels for the body-centered cubic lattice, with the exception of the inter-
changeof Psand N4. Thisis probably the result of incomplete convergence.
There is little experimental information pertaining to the Fermi sur-
face. The effective mass suggested by the optical absorption is consistent
with a negative Ed. The low position of the p levels at N suggests there
may be a substantial departure of the Fermi surface from spherical
symmetry.
19. THEKNIQHTSHIFT
The shift of the magnetic resonance line of a nucleus in the solid rela-
tive to that in a nonmetallic form, has been measured in four of the five
alkali metals: Li, Na, Rb, and CS.~* The small value of the nuclear mag-
netic moment in potassium makes observation of a resonance difficult in
that material. The shift yields a value of the quantity < I # F ( O ) ~ ~ >
where I,bF is the wave function of an electron on the Fermi surface and < >
designates the average taken over the Fermi surface.89
(19.1)
In Eq. (19.1), X P is the spin paramagnetic susceptibility (per unit vol-

ume) and 52 is the atomic volume. Uncertainty concerning the value of
X p renders the experimental determination of < I#p(0)I*> uncertain for
the heavier metals.
It often is convenient to compare < J # F ( O ) ) ~ > with J#A(O)~~
where #A
is the wave function of the valence electron in the free atom. This quan-
tity can be obtained from the observed hyperfine splitting with use of the
formula of Fermi.Qo
(19.2)
Here, AW is the hyperfine splitting in energy units, p is the nuclear mag-

netic moment in units of the nuclear magneton, pn is the nuclear mag-
neton, and P B is the Bohr magneton. The reason for introducing (I,bA(0)la
87 H. Brooks (private communication) also reports substantial negative values for E4
in rubidium and cesium.
88 W. D. Knight, Solid State Phys. 2, 93 (1956).
89 C.H.Town-, C. Herring, and W. D. Knight, Phys. Rev. 70, 852 (1950).
90 E.Fermi, Z.Physik 60,320 (1930).
144 JOSEPH CALLAWAY
is that the ratio

(19.3)
may be predicted more accurately with the use of the theory than either
quantity separately. Many of the defects in the fields may be the same
for both. #F and $A are reasonably accurately known in the lighter alkali
metals, however, the relativistic effects are of importance in cesium. A
comparison of experimental and theoretical values for < (#F(O)I~>and
I # A ( o ) [ z is given in Table XI.
TABLEXI. <I$P(o)l'> AND ] $ A ( o ) l ' (ATOMIC UNITS)

Li Na K Rb j cs
<I$p(O)]*>th 0.110," 0.110' 0.555' 0.664d 0.786" 1.76' 3.0/ 2.47'
Id'A(0)l'th 0.223," 0.242' 0.685" 0.840' 0.676# 2.18' 2.69 2.97'
6th 0.49,' 0.455' 0.8lc 0.790b 1.28 0.81' 1.21 0.832'
< I $ P ( O ) J * > ~ ~ ~ 0 . 1 0 + 0.05d 0.53k 0.05d 2 . 32d 4.39d.h
I$A(o) I*~XP 0.231' 0.751' 1.11' 2.34' 3.88'
&xp 0 . 4 3 k 0.02d 0.7055 0.7d 0 . 993h 1 .13deh
a W. Kohn, Phys. Rev. 96,590 (1954).

b Unpublished calculations of H. Brooks, quoted by G. B. Benedek and T. Kushida,
Phys. Rev. to be published.
0 T. Kjeldaas and W. Kohn, Phys. Rev. 101, 66 (1956).
d G. B. Benedek and T. Kushida, Phys. Rev. to be published.
J. Callaway, unpublished.
f J. Callaway and E. L. Haase, Phys. Rev. 108,217 (1957).
0 R. M. Sternheimer, private communication.
h Deduced from experiment using theoretical values of the paramagnetic susceptibility

according t o the work of D. Pines, Solid State Phys. 1,367 (1955).
i Determined from hyperfine structure measurements listed by W. D. Knight, Solid
State Phys. 2, 93 (1956).
i J. Callaway and D. F.Morgan, Phys. Rev., to be published found these values for Rb:
<I'#R(O)l*>th, 2.16: ]$A(0)1'th, 1.96: Eth, 1.10-
Measured values of the spin paramagnetic susceptibility are available

for lithium and sodium, and make possible an unambiguous determina-
tion of < l # ~ ( O ) 1 ~ > in these metals. For rubidium and cesium, X , has t o
be obtained from the theoretical calculation of PinesSson the basis of the
collective electron picture. The agreement between the theoretical and
experimental values of X , for lithium and sodium is good.
Kohn has computed values of $A(O) and $P(O) for lithium and so-
d i ~ mThe. ~ values
~ for lithium were obtained using Seitz's potential and
a variational method; those for sodium were obtained from the wave
91 For source references, see the notes to Table XI.
ELECTRON ENERQY BANDS IN SOLIDS 145
function of Von der Lage.g2The wave function obtained by a perturbation

theory expansion of $k (Section 2) also gives good results for in these
cases (4 = 0.46 for Li). The values computed by Callaway for potassium,
rubidium, and cesium were obtained using perturbation theory. The
values of Brooks were obtained through use of the quantum defect
method. Relativistic effects are probably responsible for the disagreement
between theoretical and experimental values of gA(0) and # p ( O ) for
rubidium and cesium. It appears that the ratio 5 is more accurately given.
Benedek and Kushida have studied the pressure dependence of the
Knight shift.g1They determined the dependence of X , on volume from
the formula of Pines and unpublished calculations of Brooks. From this,
the volume dependence of < I$p(0)12>could be computed. For lithium,
<I$p(0)12> appears to decrease with increasing volume. For the other
alkali metals, it increases with decreasing volume. The results appear to
be in good agreement with unpublished caIculations of Brooks except in
the case of cesium. In that element, the quantity < I $ p ( O ) l * > shows an
anomalously strong volume dependence: It is observed to increase by
about 50% for a change in volume of about 22%. The calculations of
Kjeldaas and Kohn for the volume dependence in sodium do not agree
with experiment as well as those of Brooks.
20. METALLIC
HYDROGEN
Although metallic hydrogen does not exist a t pressures obtainable in
the laboratory, it is of some interest as a theoretical exercise. In the
Wigner-Seitz approximation, the field within a single cell is Coulombic,
so that an analytic solution of the Schrodinger equation is possible.
Wigner and Huntington calculated the cohesive energy of metallic hydro-
gen.9aRecently the problem has been taken up by Baltenspergerg4and
Stern and TalIeyg6in connection with the problem of the impurity band.
There has also been some interest because of possible geophysical
application.
Stern and Talley found, EO = -2.041, EL?= 0.963 for T. = 1.58.96If
the cohesive energy is computed using the standard theory with these
parameters, one finds E, = 31.9 kcal/mole. It appears that significant
corrections must be made to the free electron exchange and correlation
expressions. Taking these into account, Wigner and Huntington obtained
92 F. C. Von der Lage, Ph.D. thesis, Cornell University, 1943 (unpublished).

9) E. Wigner and H. B. Huntington, J . Chem. Phys. 3, 764 (1935).
94 W. Baltensperger, Phil. Mag. [7] 44, 1955 (1953).
96 F. Stern and R. M.Talley, Phys. Rev. 100, 1638 (1955).
96 R. Kronig, J. De Boer, and J. Korringa, Physica 12, 245 (1946).
146 JOSEPH CALLAWAY
a maximum cohesive energy of 10.6 kcal/mole for r, = 1.5.9sThe energy

of the molecular form is much greater than this a t a much lower density
(52.4 kcal/mole a t a density 0.087 or r, = 2.8). However, the metallic
form might be stable under extreme pressures.
The energy of the lowest state increases, that is becomes less negative,
with increasing r, and approaches EO= -1 as r, -+ 00. The effective
mass is always equal to or greater than the free electron mass since there
are no p states in the core. Accurate calculations of higher levels have not
been made, but crude estimates based on simplified boundary conditions
show that the bottom of the 2 p band is below the top of the 1s band a t
small lattice constants. For larger lattice constants, the 1s band disengages
itself from the p band. This is analogous to the situation in lithium.
21. GENERALSURVEY AND CONCLUSIONS

The alkali metals have been emphasized in this review because the
theory is in a rather well-developed state. This is principally the result of
the simple physical situation, which allows one to determine a potential
(either explicitly or implicitly as in the quantum defect method) without
detailed knowledge of the distribution of conduction electrons.
In regard to the cohesive energy, which is perhaps the most funda-
mental quantity, it is seen that theory is able to account for the experi-
mental results within reasonable error. The precision of the experimental
determinations is somewhat difficult to estimate. The cohesive energies
are reproduced about equally well by the methods involving explicit
potentials and by those based on the quantum defect method.
The principal uncertainties in the calculations of cohesive energy
arise from features not included in a one-electron approximation, namely
the correlation between core and valence electrons, as expressed in the
polarizability problem, and the correlation energy in the free electron
sea. In regard to the polarization problem, it would be very helpful if
experimentally reliable determinations of the polarizability were avail-
able. There is also the serious problem of estimating the screening of the
polarization potential. It was mentioned previously that the lack of an
adequate expression for the energy of a free electron gas a t low density
is a great impediment. Even if Wigner’s formula for the correlation energy
is valid to within 20% for cesium, there is still an uncertainty of f4
kcal/mole which is greater than 20% of the cohesive energy. Perhaps it
is worth repeating that the recent results of Bohm and Pines, Gell-Mann,
and Brueckner do not apply at the densities actually found in the alkali
metals.
Since the correlation energy as given by Wigner’s formula varies
slowly with r8,a calculation of the lattice constant should be less sensitive
to correlation than is the cohesive energy. The agreement between the
theoretical calculation of Brooks and experiment in this respect is rather
good.
It is apparent that more experimental information concerning the
nature of the Fermi surface would be very desirable. Measurements of
the electron specific heat would give the density of states on the Fermi
surface. The measurements are complicated for lithium and sodium by
the phase transitions which occurg7at low temperature. The explanation
of these transitions is not known. Measurements should be possible for
potassium, rubidium, and cesium, however. More precise measurements
of the optical properties would be welcome, particularly in the infrared
region. Lithium and cesium need particular consideration. Finally, experi-
ments, such as the anomalous skin effect which can reveal the anisotropy
of the Fermi surface,g*would be very useful in the alkali metals.
111. Metals of Groups II and 111
22. GENERALDISCUSSION
Metals of group I1 possess two s electrons. According to the simplest
ideas concerning bands, the lowest band should be full and the materials
should be insulators. Moreover, the cohesive energy should be small com-
pared with that for the alkali metals. Actually, these substances are con-
ductors and the cohesive energies are larger than those of the neighboring
alkali metals. This behavior is explained by the fact that there is a very
considerable overlapping of bands (s and p or s and d) in the region of
the observed lattice spacing so that conduction can occur.
The problem of filling out this simple picture with quantitative detail
is quite difficult. The difficulty is principally related to the problem of
obtaining a crystal potential and treating correlations. In the first place
the potential seen by a valence electron within one cell is not the same in
the free atom and in the solid. The charge distribution of the other valence
electron is altered in going from the free atom to the solid. This accentu-
ates the difficulty of obtaining self-consistency. Some form of the valence
electron charge distribution must be assumed in order to start. Secondly,
there is the question of treating the interaction-of the valence electrons
within a single cell. These electrons can be assumed to have opposite spin
because of the presence of the Fermi hole, however, the correlation be-
tween the electrons is important and may be different in the atom and in
p7 C. S. Bsrrett and 0. R. Trautz, Trans. A.I.M.E. 176, 579 (1948).
@*R.
G. Chambera, Cun. J . Phys. 12, 1395 (1956).
148 JOSEPH CALLAWAY
the solid. We may note in passing that in the case of a trivalent atom it is
also necessary to consider the exchange interaction of the valence
electrons.
The divalent metals generally tend to have closepacked structures :
beryllium and magnesium are hexagonal, calcium and strontium are face-
centered cubic. Barium, however, is body-centered. The cohesive energy
is not expected to depend critically on crystal symmetry as is made
evident by the multitude of allotropic modification which exist in metallic
systems.aaThere is calculational evidence in support of this assertion.
Among the trivalent metals, aluminum has received most attention.
It has a larger cohesive energy and a higher electrical conductivity than
magnesium. There is considerable experimental information concerning
the band structure. Some experimental information also exists on gallium,
but its complicated crystal structure hinders calculation. The theoretical
problems are essentially the same as for the divalent elements.
23. BERYLLIUM
Studies of the cohesive energy and energy bands have been made by
Herring and Hillggand by Donovan.loo The calculation of Donovan is
considerably simpler and less involved than that of Herring, and will be
discussed first.
Donovan’s approach is an extension of the theory of the cohesive
energy considered in Part I1 (see also Section 24). It is based on the
spherical approximation, the atomic cell being replaced by a sphere, so
that no detailed account is taken of the crystal symmetry. A boundary
correction and a Fermi energy are determined; free electron values of the
exchange and correlation in the valence electron distribution are used.
The crystal potential was taken from a self-consistent field calculation;
exchange between the valence and core electrons was neglected. For
r, = 2.37, Donovan obtained E O = -0.90, Ef = +0.616. Computa-
tion of the cohesive energy is uncertain because of the effect of correlation
of the valence electrons in the free atoms. If such correlation is neglected,
the energy in the free atom on the Hartree theory can be used. This gives
96 kcal/molelO1for the cohesive energy. If the experimental value of the
energy in the atom is used, exchange and correlation will have been
included completely in the free atom but not entirely for the solid. The
cohesive energy is then decreased by 45 kcal/mole to 51 kcal/mole. The
0sC. Herring and A. G. Hill, Phys. Rev. 58, 132 (1940).
B. Donovan, Phil. Mag. [7] 45, 868 (1952).
100
101Donovan’s figures have been altered by taking the correct version of Wigner’s
correlation expression (see footnote 35). The difference amounts to 5.3 kcal/mole
for r, = 2.37.
ELECTRON ENERGY B A N D S IN SOLIDS 149
experimental value is about 75 kcal/mole. The agreement is quite reason-

able when the uncertainties of the correlation energy are included.
Donovan also obtains good results for the lattice constant and the
compressibility.
Donovan’s calculation can be criticized in several respects. No account
has been taken of departures of E(k) from the simple parabolic form.
Exchange between valence and core electrons has not been included. It
is a little surprising that the cohesive energy is given as closely as this.
The calculation of Herring and Hill on the other hand, is carried out
extremely carefully. The potential used is almost the same as Donovan’s.
A crude kind of self-consistency is obtained in both calculations.
Donovan’s calculation is self-consistent with respect to the wave function
of the lowest state. It is assumed that the charge distribution in a cell can
be represented adequately by taking it to be the same as that of the two
electrons in the lowest state. The calculation is continued until the com-
puted wave function of the lowest state $0 is the same as the $0 assumed.
Herring and Hill did essentially the same thing except that they assumed
the charge in one cell should be represented by one s and one p electron.
The accuracy of such procedures is open to question, however: the charge
distribution of the valence electrons probably is very nearly uniform so
that the errors probably are not of major significance. The cellular method
was applied to the bottom of the band and the OPW method was used for
higher states, in the vicinity of the Fermi surface. Calculations were made
for three values of the lattice parameters c and a, corresponding to
r, = 2.07, 2.37, and 2.67. (The ratio c/a was assumed to be 1.63 through-
out.) The effective mass, which was assumed to be isotropic (this is not
required by hexagonal symmetry), is in good agreement with the results
of Donovan.
Herring and Hill neglected the exchange interaction between valence
and core electrons in solving the wave equation. The interaction was
included, however, in the calculation of the cohesive energy. The varia-
tion of the exchange integrals with k was computed in this procedure.
Corrections for the lack of orthogonality of the Hartree functions were
also made. In computing the variation of the core valence exchange with
k, the wave function was obtained to second order in k. The departure
of the exchange energy of the valence electron sea from the free electron
value was also estimated and was found to be about 6% lower. The un-
certainty in the correlation may be considerably greater. The first
Brillouin zone for the hexagonal close-packed lattice is shown in Fig. 7,
and the energies are shown for certain directions in Fig. 8.
Herring and Hill constructed a function giving the density of states.
The density is shown in Fig. 9, in which it is compared with an equivalent
150 JOSEPH CALLAWAY
FIO.7. Brillouin zone for hexagonal close-packed lattice, according to Herring.18

Points and lines of symmetry are shown.
0.8
0.6
r)
0.4
0.2
0.0
FIG.8. Energy bands in Be parallel to the hexagonal (k,) axis, according to Herring
and H i l l . 9 9 The function n(k) represents the approximate ionization energy of a state.
free electron density. The effective mass a t the bottom of the band, in-
cluding exchange interaction is 1.40. It is greater than 1since there are no
p states in the core. The energy on the Fermi,surface is 0.865 ry above the
bottom of the band. The band width is 11.6 ev, compared to a free electron
value of 10 ev if m = 1.4 and 14 ev if m = 1.
The cohesive energy calculated on this basis turns out to be 53 kcal/
mole at r, = 2.37 or 58 kcal/mole if one uses the correct form of Wigner's
correlation expression. This result is obtained employing the observed

energy of the neutral Be atom and can be regarded as an underestimate.
The Fermi energy is greater than in Donovan's calculation, but this is
compensated by the more accurate calculation of the total energy.
2.0 -
n(q)
I.0-
I
.50 I .oo
3
FIQ.9. Density of states in.Be according to Herring and Hill.Qo The parabolic
curve is the density of states for free electrons with the calculated effective mass.
The dotted line is the Fermi energy. 9 is the ionization energy.
24. MAGNESIUM
Energy levels for magnesium have been calculated by Raimes102 and
Trlifai.lo* The work of Raimes, which preceded that of Donovan on
Betloois very similar to the latter.
The calculation is of the Hartree type, exchange between core and
valence electrons being neglected. The potential is taken from a self-
consistent field. A crude kind of self-consistency was obtained, as dis-
cussed in the preceding section. The zone structure is neglected and the
band is assumed to be parabolic throughout. For T, = 3.35, Raimes ob-
tained Eo = -0.67, Ez = 1.29. The difficulty, found in beryllium in re-
gard to the cohesive energy, is also present in this case. A value of the
energy in the free atom must be chosen; this is uncertain because of the
correlation energy. If the value obtained from a Hartree calculation is
used, the cohesive energy should be overestimated. When this figure
is used, a cohesive energy of -8.7 kcal/mole (no binding) is obtained for
T, = 3.35. The experimental cohesive energy is 38 kcal/mole. The dis-
lo* S. Raimes, Phil. Mag. [7] 41, 568 (1950).

101 M. Trlifaj, CzechosZov. J . Phy8. 1, 110 (1952).
152 JOSEPH CALLAWAY
crepancy must be ascribed to the defects of the method, that is to the

neglect of exchange and the assumption of a parabolic band. Raimes does
obtain a cohesive energy of 25 kcal/mole for rS = 4.16. His calculated
compressibility is reasonable. It would appear that the simple method of
estimating the cohesive energy should not be extended beyond beryllium.
Raimes has extended his treatment to all the divalent rnetals.lo4
Additional approximations are introduced. The experimental value of the
second ionization potential of the free neutral atom is used in a manner
similar to that employed by FrohlichIo6 to determine the energy of the
lowest state. The equilibrium lattice constant and the cohesive energy
state are obtained, based on this information. An explicit potential is not
constructed. All the bands are assumed to be parabolic and to have the
mass ratio Ez = 1. The calculated values of lattice constants and com-
pressibilities are fair agreement with experiment, but the lattice constant
tends to be too large. The cohesive energies are rather poor. It is difficult
to single out the major source of error, but it probably is the use of the
free electron Fermi energy for a parabolic band. It is unlikely that the
band has nearly parabolic form, particularly in the heavier alkaline
earths and in the metals of group IIb.
Trlifaj lo* applied to magnesium a method developed by Matyaslo6
which combines an early form of the augmented plane wave method of
Slaterlo7and the statistical approach of Gombis.los A group theoretic
analysis was used to determine the symmetries of wave functions at vari-
l ~ ~analysis is based on the use of a zone twice
ous points in the ~ 0 n e . The
the size of that employed by Herring. A simple semiempirical potential
of analytic form was employed. In the approach of Gombis, it is assumed
that the valence electrons are distributed uniformly. The energy of inter-
action of this distribution with the ions is calculated and a potential is
included to represent the resistance to intrusion of the valence electrons
into the electron shells of the ions. This is done to include the effects of
orthogonalizing the valence electron wave functions to those of the core.
The ordinary potential of the ion is included, of course, either empirically
or with the use of Hartree’s calculations. Exchange and correlation inter-
actions in the free electron distribution are also included.
I04 S . Raimes, Phil. Mag. [7] 4S, 327 (1952).

106 H.Frohlich, Proc. Roy. SOC.(London)Al68, 97 (1937).
106 2. Matyaa, Czechoslov.J . Phys. 1, 3 (1952).
lo7 J. C . Slater, Phys. Rev. 61, 846 (1937).
108 P. Gombh, “Die statistische Theorie des Atoms und ihre Anwendungen.” Springer,
Vienna, 1949.
109 E. Antoncik and M. Trlifaj, Czechoslov.J . Phys. 1, 97 (1952).
Trlifaj calculated the energy associated with iifteen irreducible repre-
sentations at ten symmetry points of the zone. The results were used to
construct a density of states. The result shows a close qualitative resem-
blance to those obtained from the soft x-ray emission. It is illustrated in
Fig. 10. A total band width of 6.3 volts, which is in good agreement with
the experimental value of about 6.5 ev, was obtained. A rise in the x-ray
spectrum is seen to occur a t an energy which corresponds closely with
the predicted onset of transitions from the second zone. A maximum
which corresponds to the highest level density in the first zone may also
ENERGY (RYDBERGS)
Fro. 10. Density of states for Mg according to Trlifaj.'oa
be noted. The cohesive energy calculated on this basis, namely 44 kcall

mole, is in good accord with the experimental result.
The agreement with experiment is very satisfying. The correctness of
the calculation is a little di5cult to assess. There is no reason, other than
one based on comparison of results, for believing that Gombas' approach
really is applicable to divalent and trivalent metals. Moreover, Trliiaj
does not give enough evidence to judge the convergence of the perturba-
tion method he employed. A calculation for a simple metal, such as an
alkali, in which comparison with other work would be possible, would be
very desirable. Matyas has promised such a paper, but apparently it has
not appeared. Finally, it is not clear how carefully the density of states
was constructed. The significance of agreement between the shape of a
calculated density of states and one obtained from the soft x-ray emission
curve is also somewhat uncertain, since there are unresolved discrepancies
even in the simple case of lithium.
154 JOSEPH CALLAWAY
25. CALCIUM
Energy bands in calcium were studied by Manning and Krutter in
an early calculation."O The potential was based on a self-consistent field
without exchange. The potential of a valence electron whose charge den-
sity was normalized to the atomic volume was added to the potential of
the ion core. Exchange interactions between core and valence electrons
were not included. The calculation was made in accord with the early
form of the cellular method. The boundary conditions were not fitted
with sufficient accuracy. The results have little quantitative significance.
In particular, the fivefold degeneracy of the d levels that obtains in the
free atom has not been removed a t the center of the zone. The entire
shape of the d band is probably quite different from that obtained by
Manning and Krutter. The authors found a small overlap between the
s and d band, which accounted for the metallic properties of calcium. An
approximate density of states which has been copied in several standard
references was constructed. The rapid rise in this function at the pre-
sumed bottom of the d band is in part a consequence of the fact that the
fivefold degeneracy was not removed, and should not be taken too
seriously.
26. ALUMINUM
The energy bands in aluminum have been studied by several au-
thors. ln-l10 Considerable experimental information is also available.
The calculation of Matyaslll was based on a tight binding approxima-
tion using one s function and three p functions. Potential integrals with
first neighbors alone were included. The effects arising from the lack of
orthogonality of wave functions on different atoms were not considered.
The interaction integrals were not calculated directly, however, some were
estimated from x-ray data. An approximate density of states was pro-
posed which is in qualitative accord with that obtained from the x-ray
emission spectrum. The calculation cannot be expected to yield quantita-
tive information because of the magnitude of the approximations involved.
Gasparlla and Antoncik"' have applied methods based on the work of
Gombasgsto aluminum. Different forms of the potential representing the
effective repulsion of the core electron shells for the valence electron were
M. F. Manning and H. M. Krutter, Phys. Rev. 61, 761 (1937).
2. Matyas, Phil. Mug. [7] 59, 429 (1948).
11* R. Gaapar, Acta Phys. Acad. Sn'. Hung. 2, 31 (1952).
l l * S. Raimes, Proc. Phys. Sx.(London) 00,949 (1953).
114 E. Antoncik, Czechosloy. J . Phys. 2, 18, 31 (1953).
116 V . Heine, Proc. Roy. SOC.(London) A240, 340, 354, 363 (1957).
used. The results agree reasonably well with experiment in both cases.
Antoncik haa also applied the method of M ~ t y a to s ~determine
~ energy
levels for some of the lowest states at five symmetry points of the zone.
A function for the density of states was also constructed and the results
were compared with those obtained from the soft x-ray emission. A band
12.2 volts, in width, was obtained. Most of the comments made in Section
25 regarding the calculation of Trlifaj also apply here.
Raimes extended his semiempirical treatment of the divalent meta1s104
to a calculation of the compressibility of metallic aluminum. The equilib-
rium lattice constant and energy of the ground state are found from the
third ionization potential of the free neutral atom. The Fermi energy and
Coulomb interaction were computed assuming the electrons are free.
The agreement of the cohesive energy and lattice constant with experi-
ment is rather poor; the relation between the compression and pressure is
rather satisfactory. The use of the semiempirical method for obtaining
r, does not seem to be well justified.
Heine has reported a very careful study of the energy bands in alumi-
num in a series of three papers. The results of two calculations in which
different potentials are used, are presented. He has also been abIe to inter-
pret the experimental data in terms of a detailed model of the band struc-
ture. Following Heine, the experimental information is considered first.
This comes principally from measurements of the de Haas-van Alphen
effect,lI6 and is supplemented by measurements of the anomalous skin
effect"' and the low-temperature specific heat.ll8
The period of the oscillation of the diamagnetic susceptibility, when
regarded as a function of 1/H, determines the area in k space of an
appropriate cross section through the part of the Fermi surface responsi-
ble for the effect. It is possible to determine the shape of this portion of
the Fermi surface by varying the orientation of the field with respect to
the crystal axes. Two sets of oscillations have been observed in aluminum:
high-frequency oscillations arising from sections of the surface which
contain 0.6 X lo-* electron or hoIes per atom, and low-frequency oscilla-
tion associated with sections containing 5 X loT6electron per atom. The
effect of the main part of the Fermi surface has not been observed. The
anomalous skin effect, which has been studied only for polycrystalline
samples, gives the total area of the Fermi surface. The low-temperature
specific heat yields the density of states at the Fermi level.
If the free electron model were exact, the first Brillouin zone would
116E. M. Gunnersen, Phil. Trans. Roy. SOC.A249, 299 (1957).
117T. E. Faber and A. B. Pippard, Proc. Roy. SOC.(London)A2S1,336 (1955).
ll*D. H. Howling, E. Mendoza, and J. E. Zimmerman, Proc. Roy. Soc. (London)
A229,86 (1955).
156 JOSEPH CALLAWAY
be full and the second half full. The energy surfaces would be caps of
spheres having their convex sides toward the center. Heine interprets the
observations to indicate that the surface is deformed around the zone
corners so that pockets of holes and electron exist in the vicinity. The
area of the Fermi surface tends to be larger than would otherwise be
expected because of this deformation. The shape of the pockets of holes,
which give rise to the high-frequency oscillations mentioned previously,
has been determined from experiment and is consistent with the situation
expected in the neighborhood of the square face centers X or the corners
W. As will be seen, there are theoretical reasons for preferring W . The
location of the electrons which produce the low-frequency oscillation has
not been determined experimentally, but it probably is also close to W,
perhaps along the line W X .
The first of the band calculations reported by Heine was made using
the OPW method and a potential obtained from a self-consistent field
without exchange for AP+. Core valence exchange was not included in
this calculation. Levels were calculated for 15 irreducible representations
a t r, L, X , W, and K . In addition, 140 more general points were studied.
The results indicate that E(k) is very close (within 0.01 ry) to the free
electron values except close to the zone surface. This calculation indicates
that the first zone should be completely filled, and the third and fourth
zones almost unoccupied.
The more accurate band calculation was based on a crystal potential
which was constructed very carefully. The contribution of the AP+ cores
was obtained from a recent calculation which included exchange. A correc-
tion made for correlation effects among the core electrons was determined
by analogy with a calculation carried out by Bernal and Boys for so-
di~m.11~ Separate core-valence exchange potentials were computed for
s and p states. The contribution of the valence electrons to the crystal
potential was calculated assuming that the wave function for the valence
electrons are single OPW’s. This potential resembles that of a uniform
charge distribution but departs from it by small but possibly significant
amounts. Comparison of the assumed potential with that computed from
the wave function finally obtained indicates that the work is very nearly
self-consistent. A correction was applied to take account of the departure
of the potential from that of a uniform spherical model, since the actual
charge distribution in the metal does not consist of overlapping spheres of
charge which drop to zero at the sphere radius. Exchange among the
valence electrons was included by employing the results of Bohm and
Pines. This energy was determined as a function of k, and the variation
with r was also determined for states on the Fermi surface. The resulting
119 M.J. M.Ekrnal and S. F. Boys, Phit. Trans. Rw. Soc. A246, 139 (1952).
crystal potential appears to be the most carefully constructed one used

for a multivalent atom. Appropriate core functions were found by numeri-
cal integration for this potential. The OPW calculation appeared to be
convergent within 0.02 ry.
Except in the vicinity of the Fermi surface, E(k) is close to the free
electron values for the case in which the effective mass m* = 1.03. The
results do not agree in detail with the model deduced from experiment,
in the sense that the levels at the corner in the first zone appear to be
TABLEXII. ENERGY
LEVELSIN ALUMINUM,ACCORDING
TO HEINE
State Calculation I Calculation I1 (position relative to rl only)

8 band
rl -0.637 0.000
LI 0.086
x1 0.288 0.929
Ki 0.311, 0.441 0.966, 1.298
Wl 0.613 1.182
p band
L2* 0.047
Xt 0.230 0.806
KaI 0.313 0.925
Wa 0.399 1.012
w21 0.404 1.063
Fermi level 0.48 (approx) 1.083
d band
1.44
slightly (0.07 ry) below the Fermi surface instead of above it. The calcula-
tion does not predict the existence of pockets of holes. The levels at the
center of a square face are substantially below the Fermi surface, so that
if they do exist, it is likely that such pockets are located around the cor-
ners. The effective masses and the length of axes of the pockets can be
calculated if it is assumed arbitrarily that pockets of holes do exist there.
The results agree with experiment in order of magnitude but not in
quantitative detail. The effective masses are small because the levels at
the corner are close. This is as required by experiment. It is worth men-
tioning that, in both calculations, the relative order of levels in the s and p
bands agrees with the normal level order for the face-centered lattice.
The results are presented in Table XII. The total band width is 14.7 volts
which is somewhat greater than the value of 10.6 volts obtained from soft
x-ray emission spectra.
158 JOSEPH CALLAWAY
It is not known whether the quantitative discrepancies with experi-

ment can be explained in terms of residual defects in the crystal potential,
such as the neglect of a core polarization potential, or whether correlation
effects among the valence electrons must also be considered in detail.
27. SOLID HELIUM
Ten Seldam has estimated the interatomic distance at which a model
of solid helium would become a metal.lZ0He assumed that solid helium
would have the face-centered cubic structure at high pressures. The goal
of the analysis was to determine the distance a t which the bands would
overlap so that some levels in the second zone would be below those in
the first. The calculation was made by expanding the wave function in
symmetrized combinations of plane waves. There are no core states to
give trouble in orthogonalization. A potential for a neutral lattice of
helium atoms was taken from a self-consistent field. Various methods of
selecting the valence electron exchange were tried. Energy values were
obtained for representations WI and LZlusing determinants to 10th order,
and the results for infinite order were estimated. Calculations were made
for three values of the atomic radius; W1 belongs to the s band and is at
the top of the first zone; L+ is a t the bottom of the second. The difference
in energy of the levels is quite sensitive to the choice of exchange poten-
tial, Using the potential believed to be most realistic, it appears that a
pressure of 207 mega-atmospheres would be required to cause the energy
of Lr to be lower than that of WI and so produce metallic behavior. The
results are quite sensitive to the exchange interaction.
IV. Elements o f Group IV and Related Semiconductors
28. GENERALCONSIDERATIONS
There has been a considerable effort, both experimental and theoreti-
cal, to determine of the band structure of group IV elements. This effort
is, in the main, a result of the development of semiconductor devices. A
great deal of progress has been made, and many detailed features of the
band structures of germanium and silicon have been determined. Graph-
ite has also been studied rather intensively, as have some of the 111-V
compounds.
It has been possible to understand many of the electrical and optical
properties of these materials in terms of specialized band models. The
experiments are mutually consistent. This success of a one-particle model
in a very gratifying confirmation of the theory of energy bands. The rea-
120 C. A. Ten Seldam, Ptuc. Phys. Soc. (London) A70,97,529 (1957).
sons for expecting a one-particle theory to work under these circumstances
were mentioned briefly in Section 2. It is worth restating that semicon-
ductors and insulators are intrinsically simpler than metals theoretically
because a small number of particles participate in conduction processes
and there is an energy gap between the vacant and the occupied one-
electron states. This gap, which provides a nonvanishing minimum
energy denominator in the formulas of perturbation theory, reduces the
effect of the electron interaction. For this reason, the quantitative applica-
tion of the theory of energy bands should meet its greatest success for
these materials. One must confess, however, that the predictions of theo-
retical calculation have been somewhat disappointing when compared
quantitatively with experiment, although there have been marked quali-
tative successes. Much additional theoretical work of the most careful
kind will be required to determine whether the one-electron theory can
really yield accurate quantitative results. Most of the present difficulties
appear to be connected with the problem of obtaining self-consistency : a
band calculation must be based on an assumption concerning the distribu-
tion of the valence electrons which are under study. In this respect, the
simple approximation based on the use of a uniform distribution of
valence electrons within one cell is much less valid than in the mono-
valent, divalent, and trivalent metals studied, for the binding is of
covaIent rather than metallic character.
29. GRAPHITE
There have been a number of calculations of energy bands in graph-
ite,121-12s
which crystallizes in layers. The atoms are arranged in hexagons
in each layer. The spacing between layers is considerably greater than
that between atoms in a given layer. Many of the electrical properties, for
example, the conductivity, exhibit large anisotropies. A two-dimensional
model of a single layer has often been the object of study. Calculations
based on such a model may give qualitatively reasonable explanations
of the experimental facts. There is covalent bonding between the atoms
in each layer. In fact a layer may be imagined to be a large aromatic
molecule, whereas the binding between planes is of van der Waals
121 P. R. Wallace, Phys. Rev. 71,622 (1947).
C. A. Coulson, Nature 169, 2651 (1957).
1 2 1 C. A. Coulson and R. Taylor, Proc. Phys. SOC.(London) A M , 815 (1952).
I f 4 J. L. Carter and J. A. &umhansl, J . Chem. Phys. 21, 2238 (1953).
125 J. C. Slonczewski and P. R. Weiss, Phys. Rev. 99, 636 (1955); 109, 272 (1958).
126 W. M. Lomer, Proc. Roy. SOC.(Lmdon)A227, 330 (1955).
127 D. F. Johnston, Proc. Roy. Soe. (London) A227, 349, 359 (1955); A237,48 (1956).
I** F. J. Corbato, Ph.D. Thesis, Massachusetts Institute of Technology, 1956 (un-

published).
160 JOSEPH CALLAWAY
character. The calculations generally have employed the tight binding

approximation.
The early work of Wallace,121although primitive in some respects,
furnishes a simple model in terms of which many experiments can be
interpreted. The basis of his analysis is that only a single layer need be
considered. The unit cell for such a layer contains two nonequivalent
atoms, and the Brillouin zone is the hexagon shown in Fig. 11. Points and
lines of symmetry are indicated according to the notation of Lomer,126
who has analyzed the symmetry properties of the wave functions in detail
Q P
FIQ.11. Brillouin zone for a graphite layer after Lomer.1*6

The carbon atoms are considered to be in the configurationpa.The orbitals
which are formed from functions of symmetry 8, p,, and pv, lie in the
plane (u). Such orbitals are fully occupied and do not contribute to con-
duction processes. The fourth electron has a wave function with sym-
metry p.; these orbitals are perpendicular to the layer (a).The 1 electrons
are responsible for conduction; it will be seen that both holes and electrons
exist in the band. Wallace considered only potential integrals between
a-electron wave functions on nearest neighbors of both kinds, which he
carried as undetermined parameters. He neglected the nonorthogonality
of functions centered on different atoms. In this way, one obtains a
parameterization of the band structure of graphite which, although
crude, indicates some of the most important features. The basic point is
that there is degeneracy at the point P between the filled and the empty
a bands. This is a consequence of the symmetry of the layer model. At
absolute zero, the lowest r band would be full, the upper one empty; how-
ever, there is no energy gap. The energy depends linearly on (k-k,l in the
vicinity of P.
ELECTRON ENERGY BANDS IN BOLIDS 161
The most detailed theoretical calculation based on the single layer
model is that of Corbato.lZ8The other calculations employ rather unjusti-
fied approximations in the interest of simplifying the tight binding
scheme to permit easier calculation. In Corbato's calculation, Bloch func-
tions were formed from Is, 29,and 2 p orbitals taken from a self-consistent
field for the spa configuration of the free carbon atoms. The crystal poten-
tial was taken to be the sum of spherically symmetric potentials on each
atom; the potentials were derived from the self-consistent field. Exchange
effects were not included.
Two-center overlap and potential integrals were included through
ninth neighbors; three-center potential integrals were included through
fourth neighbors. The entire calculation, including the computation of
the integrals and the solving of the secular equation, was programmed for
a digital computer. Solutions were found along the symmetry lines p, q,
and T . There is a minimum gap of about three-fourths of a rydberg unit
between the bands formed by the u electrons. The r bands tend to lie in
this gap (the degeneracy at P is contained in it), but overlap the u bands
in the vicinity of the center of the zone. Omission of the 1s Bloch functions
was found to induce important changes, particularly in the u bands. This
raises a question concerning the effect which would be encountered if
excited wave functions (39,3 p ) were included.
It is worth remarking that the large static diamagnetic susceptibility
of graphite can readily be explained in terms of the layer model as origi-
nating in the large gradient of the energy in the vicinity of P.
Calculations which take account of the real three-dimensional nature
of the graphite crystal have not been performed in as much detail as the
work on layers. In this case, there are four atoms in the unit cell, two
associated with each layer. The Brillouin zone is a thin hexagonal prism
shown in Fig. 12.It has been standard to consider the four bands formed
from 2P, orbitals on the four atoms in the unit cell. The interaction be-
tween r and u orbitals is neglected, except in the most recent calculation
of Johnston.127This approximation may be adequate for a treatment of
the bands near the Fermi surface, since, according to Corbato, this is
located in the gap between the u bands. It cannot be expected to give a
good description of the bands throughout the zone.
The interaction between layers removes some of the degeneracy pre-
dicted by the layer model for the edges HKH and H'K'H'. The splittings
are small; of the order of tenths of an electron volt; but this is large com-
pared to kT and consequently vital in any detailed considerations of
transport properties. Wallace's three-dimensional calculation,121which
took only nearest neighbor interactions into account, yielded a conduction
band which was degenerate with one valence band along a zone edge.
162 JOSEPH CALLAWAY
He found no overlap of conduction and valence bands. Calculations by

Johnston127which included more distant neighbors, revealed additional
degeneracies near the zone edge, a small overlap between valence and
conduction bands slightly off the edge, and determined the dependence
of E on kz along the edge.
A tight binding study of the band structure of a rhombohedra1 form
of graphite has recently been reported by Haering.lZ8”
I /
H‘
FIQ.12. Brillouin zone for graphite (three-dimensional).
Much recent work has been based on a model developed by Slonczewski
and Weiss.lzs Since the interesting part of the zone extends only 1% of
the way from the edge of the zone to the center, perturbation theory is
useful. The Hamiltonian is expressed to first order in the parameter x, the
shortest vector from the edge of the zone to the point of interest through
the use of k * p perturbation theory (see Section 6). The k, dependence is
taken into account by a Fourier series, which is equivalent to the tight
binding approximation for this direction. The resulting Hamiltonian con-
tains six parameters, of which yo, the only one that appears in a layer
calculation, is much larger than the others. The parameters are to be
determined empirically to fit the results of experiment. M c C l ~ r e and
l~~
Noziereslso have applied the Slonczewski-Weiss model to detailed con-
siderations of the de Haas-van Alphenlal effect and cyclotron reso-
nance,1a2Ja8respectively. These studies are similar in many respects,
l**a R. R. Haering, Can. J . Phys. 36, 352 (1958).
1*9 J. W. McClure, Phys. Rev. 104, 666 (1956); 108, 612 (1957).
180 P. Nozibes, Phys. Rev. 109, 1510 (1958).
111 D. Shoenberg, Phil. Trans. Roy. SOC.246, 1 (1952).
J. K. Galt, W. A. Yager, and H. W. Dail, Jr., Phys. Rev. 103, 1586 (1956).
I** B. Lax and H. J. Zeiger, Phys. Rev. 106, 1466 (1957).
although there are some significant differences. The de Haas-van Alphen

effect measurements reveal the existence of both holes and electrons in
the band structure, the effective masses being 0.070 mo for holes and
0.036 mo for electrons. The observed masses are very anisotropic. The
FIG.13. Energy bands in graphite along the line KH parallel to the k, axis, accord-
ing to Nozieres.lSo The band Ea is doubly degenerate; the bands E l and E2are non-
degenerate. The separation between E I and EZa t K is about 0.6 ev; that between Ea
and El and E2a t H is about 0.025 ev. The dashed line Ep marks the position of the
Fermi level. El is about 0.02 ev below the Fermi level a t H and about 0.01 ev above
it at K.
mass perpendicular to the kz axis is much smaller than that parallel to

it (m,/m,, = 0.005 or less for both holes and electrons.) The number of
carriers effective at low temperatures is very small, of the order of 10-6
per atom.
The energy bands calculated by McClure and Nosieres exhibit a sim-
ple sinusoidal dependence of the energy on k, along a zone edge (see
Fig. 13). Two bands are degenerate along this edge. Away from the edge,
the degeneracy is removed, and an overlap between valence and conduc-
164 JOSEPH CALLAWAY
tion bands is produced so that holes and electrons can exist a t T = 0.

The energy surfaces near the edge are warped and anisotropic. As an
illustration of the complicated behavior near the edge, a model of the
Fermi surface proposed by McClure is shown in
Fig. 14. Nozieres predicts a continuous distribu-
tion of electron effective masses between 0.054
mo and 0, and a distribution of effective masses
for holes ranging from 0.066 mo to 0.054 ma. He
h d s that this distribution is consistent with the
de Haas-van Alphen effect measurements and is
able to explain all the lines in the cyclotron res-
onance data. It is likely that further detailed
analysis of cyclotron resonance, the de Haas-
van Alphen effect, and the static diamagnetic
susceptibiIity will ultimately yield a consistent
characterization of the energy bands based on
the Slonczewski-Weiss Hamiltonian.
Haering and Wallace have studied the elec-
trical and magnetic properties of graphite using
a three-parameter model derived from the tight
binding approximation.18aa The principal fea-
tures of their model are a relatively large number
of electrons per atom at low temperature (10-4)
implying a relatively large Fermi energy (about
FIG. 14. Fermi surface in
graphite according to
0.06 ev), a large value for 70 (about -2.5 or
McClure. -2.6 ev) and a small out-of-plane exchange
integral. This model is in good agreement with
the high-temperature magnetic susceptibility, the anisotropy of the con-
ductivity, and the low-temperature Hall coefficient. It does not, however,
predict the presence of holes in addition to electrons.
30. DIAMOND
There have been many calculations of energy bands in diamond. 134-141
Interest in diamond originates not only in its interesting mechanical,
1Ja R. R. Haering and P. R. Wallace, Phys. Chem. Solids 5, 253 (1957).
1x4 G. E. Kimbal, J . Chem. Phys. S, 560 (1935).
I S S F . Hund and B. Mrowka, Ber. Verhandl. s&h. Akad. Wiss. Leipzig, Math.-
natumiss. KZ. 87, 185 (1935).
18%A. Monita, Sn'. Rpts. T6hoku Univ., First Ser. 85, 92 (1949).
1117 F. Herman,Phys. Rev. 88, 1210 (1952); 95, 1214 (1954).
1 a s L . A. Schmid, Phys. Rev. 92,1373 (1953); Am. J . Phys. 22, 255 (1954).
119 G. G. Hall, Phil. Mag. t71 43,338 (1952).
140 J. C. Slater and G. F. Koeter, Phys. Rev. 94, 1498 (1954).
141 V. %Her, Ann. Phgeik [S]lS, 229 (1953).
ELECTRON ENERQY BANDS I N SOLIDS 165
electrical, and optical properties, but also in the circumstance that the
semiconductors of principal importance, silicon and germanium, have the
same crystal structure. Most of the earlier work13c13sis only of historical
interest.
Schmidl38 has calculated the cohesive energy of diamond. He started
by defining two-electron functions with which to represent a bonding lobe.
The two-electron wave function contains two parts. One part describes
the case in which an electron is on each atom of the bonded pair. In the
other, both electrons are on the same atom, one atom being ionized. The
complete crystal wave function is an antisymmetric combination of such
functions. The energy of the crystal is calculated with these functions. An
arbitrary constant A giving the ratio of the two parts of the two-electron
functions is varied so as to minimize the energy of the system. The effect
of a very complicated configuration interaction process is obtained in this
way. The basic orbitals which compose the two electron functions were
taken from a self-consistent field calculation. They were combined to have
the proper directed character, and adjusted so that functions on different
atoms were orthogonal to a good approximation. If the constant A is
set equal to zero, no binding is obtained, as is expected from work on
the hydrogen molecule. 14* The process of minimization yields a value
A = 0.82 f 0.06 and a cohesive energy, relative to the ground state of
free carbon, of 0.28 f 0.30 rydberg per atom for the system. Much of
the uncertainty of the calculation arises from the orthogonality correc-
tion. The experimental value of the cohesive energy is rather uncertain,
but lies between 0.24 and 0.54 rydberg per atom (75 and 169 kcal/mole).
Schmid's calculation does not include consideration of the energies
of the electronic states. Herman has made a rather detailed investigation
of the energy bands in diamond, utilizing the OPW method. The
crystal potential was determined as follows. Neutral carbon atoms, in the
(2s)l(2p)* 6S configuration, were arranged in a diamond lattice with the
observed lattice constant. The crystal charge density was then taken to
be the spatial sum of the atomic charge densities, the latter being ob-
tained from a self-consistent field. An approximate exchange potential
was included by using Slater's free electron average.'* The core states
employed in the orthogonalization procedure were also taken from the
self-consistent field. Energy values were calculated at the three symmetry
points: I', X, and L. The Brillouin zone is the same as for the face-cen-
tered cubic lattice. The effective masses associated with some of the
states at the center of the zone were computed.
In the tight binding approximation, the levels at the center of the zone
may be represented as bonding or antibonding combinations of a and p
14*J. c. Slater, J . Chem. Phy8. 19, 220 (1961).

166 JOSEPH CALLAWAY
orbitals on the two face-centered-cubic lattices that compose the diamond

lattice. It was found that the convergence of the OPW expansion was
much more rapid for those states (rl,I'i,etc.) which must be made orthogo-
nal to the core states, whereas the p states, which are orthogonal to the
core states MIa result of symmetry, did not converge very well. There is a
question concerning the consistency of the potentials used for valence and
core electrons. Herman neglected this problem; however, this neglect
does not seem to have had serious consequences. The minimum gap be-
tween valence and conduction bands was found to be about 6 volts. The
valence band has a width of 22 volts. The results of calculation are reason-
ably consistent with the experimental ones; however, exact values are not
known.
It is interesting to note that one of the conduction bands has a nega-
tive curvature in the 100 direction a t k = 0, so that the minimum of the
conduction band is not a t the origin, but very possibly along the 100 axis.
The maximum of the valence band lies a t k = 0; the curvature there is
negative and greater than that of the conduction band, so that the mini-
mum vertical separation between the bands probably is at k = 0. Such
a band structure has not been verified experimentally for diamond, but is
found in silicon.
Slater and Koster have applied a tight binding interpolation scheme
to determine the energy bands along the 100 and 111 axes in diamond.
The parameters required were obtained from Herman's OPW calculation.
The analysis leads to effective masses in disagreement with those cal-
culated by Herman in the two directions. In addition, their work suggests
that the lowest valence band has negative curvature a t the center of the
zone, whereas the effective mass there probably is quite close to 1. It may
be concluded that the tight binding interpolation scheme proposed by
Slater and Koster does not yield quantitatively accurate results for this
case.
The description of the wave functions for the diamond lattice that is
given by a simple tight binding approximation is very useful for qualita-
tive purposes and will be summarized here, following Slater and Koster. 140
The arguments apply to germanium and silicon as well, with very little
change. Four orbitals, one s, and three p functions are considered for each
of the two atoms in the unit cell. Eight bands can be formed from them.
At the center of the zone, we find that the lowest level is rl, which is a
combination of s functions that is symmetric about the midpoint of a
line joining the two atoms. I'Z5t, which is a symmetric combination of
the p orbitals on the two atoms, is a t the top of the valence band. The
lowest state of the conduction band is r15,which is an antisymmetric
combination of the same p orbitals. The highest is I'r, which is an anti-
symmetric combination of the 5 orbitals. Away from the center of the
zone, 5 and p functions are mixed on the different lattices. On the 100 axis
(direction k,), the function A 1combines the s and p , functions (separately)
on the two atoms in a symmetric way, whereas A21 combines the same
functions in an antisymmetric manner. The ratio of the coeficients of
the s and p combinations is, of course, a function of k and has to be deter-
mined by solving the band problem. The other band that is formed on
this axis is A5, which is doubly degenerate. This function contains a
+
combination of the p , and p . orbitals on a given atom (py p , or p , - p.)
admixed with similar function obtained from its neighbor in the unit cell.
At the face center X(lOO), all wave functions are doubly degenerate.
In X1 an s function on one atom is combined with a p, function on an-
other. The A6 band goes into Xd. At the point L, the state LI is composed
of a combination of s functions and p functions having the symmetry
+ +
x y z which is symmetric between the two atoms. LZIis a similar
combination which is antisymmetric. There also are the doubly degenerate
states Lt and Lag, which are formed respectively as symmetric and anti-
symmetric combinations of functions on the two atoms having the sym-
metry x - y and z - 8 ( x y). +
Zehler141has studied the energy bands in diamond with both the
cellular method and a variational technique involving plane waves.
He found rather large errors in the empty lattice test even when com-
plicated expansions involving Kubic harmonics were employed. The
crystal potential was obtained from a self-consistent field; however,
a uniform distribution of the valence electrons was assumed. Energy
levels were determined a t the center of the zone and at the point X. The
order of levels a t these points is essentially in agreement with that of
Herman. Minima along the 100 axis were not obtained. A band width
of 18.5 ev and a band gap of 5.9 ev were found. The large errors in the
empty lattice test render the results somewhat uncertain, especially for
the point X. The variational technique band on plane waves, which was
used for the states delineating the band gap, should be equivalent to
Herman’s procedure.
Casella has considered the energy bands in a hypothetical carbon
metal of the face-centered cubic structure.142aThe lattice constant was
chosen so that the hypothetical material would have the same average
electron density as diamond, and consequently is smaller than for
diamond by a factor of 2t. The crystal potential was taken from a self-
consistent field for the ( 2 ~ ) ~ ( 2 paP
) ~configuration of the free atom, and
exchange was included according to Slater’s free electron approximation.
The OPW method was used to compute energy levels at the center of the
14fo R. c. Casella, Phys. Rev. 109, 54 (1958).
168 JOSEPH CALLAWAY
zone r, the face centers X and L, and the midpoint of the 100 axis A.
The 1s core wave function was determined variationally for the crystal
potential used. The convergence of the OPW expansions seems to be
quite satisfactory for most states. The order of the s and p levels is con-
sistent with the normal level order in the face-centered cubic lattice.
The bands appear to be nearly parabolic with an average effective mass
m* = 1.13. The energy discontinuities across the faces of the first
Brillouin zone are small. An attempt to compare the cohesive energy for
this structure with that for diamond (based on Herman's calculations)
did not lead to a definite result.
31. SILICON
There have been a number of calculations of energy bands in sili-
C O ~ . A ~ substantial
~ ~ - ~ ~amount
~ of experimental information which gives
a reasonably detailed picture of the band structure has been accumu-
lated. A number of basic papers are listed, with no attempt a t com-
pleteness.lS1-l 67
It probably will be convenient for the reader to keep the experimental
band structure information in mind and to use it as a guide in evaluating
the results of theory: the width of the valence band is about 17 volts.1Ss
The lowest state in this band is rl, and the highest (in the absence of spin
orbit coupling) is I'45t. Actually spin orbit coupling2' splits the sixfold
degenerate level (including the spin degeneracy) into a fourfold
degenerate state rg+ which is at the top of the band and a doubly
degenerate state r7+which is depressed by about 0.04 ev. At points
148J. F. Mullaney, Phys. Rev. 66, 326 (1944).

144D. I(. Holmea, Phys. Rev. 87,782 (1952).
14sE.Yamaka and T. Sugita, Phys. Rev. 90,992 (1953).
146T.0. Woodruff, phys. Rev. 98, 1741 (1955); 108, 1159 (1956).
147D. P. Jenkins, Proc. Phys. Soc. (London)A69, 548 (1956); see also D. G. Bell,
R. Heneman, D. P. Jenkins, and L. Pmcherle, Proc. Phys. Soc. (Lorrdon) A67, 562
(1954).
140 F. Bassani, phys. Rev. 108, 263 (1957).
149F. Herman, Proc. Z.R.E. 11, 1703 (1955).
150 E. 0. Kane, J . Phys. Chem. Solids 1, 83 (1956).
161 G. Dreaselhaus, A. F. Kip, and C. Kittel, Phys. Rev. 98,368 (1954).
161 G. L. Pearson and C. Herring, Physica 20,975 (1954).
168 A. H.Kahn, phys. Rev. 97, 1647 (1955).
164 G. G. Macfarlane and V. Roberts, Phys. Rev. 98, 1865 (1955).
166 H. Y. Fan, Solid Stde phys. 1, 283 (1955).
166 D. H. Tomboulisn and D. E. Bedo, phy8. Rev. 104,590 (1956).
167 W. C. Dash and R. Newman, Phys. Rev. 99, 1151 (1955).
sufficiently close to the top, the E(k) relation can be written:

h2
E1,2(k) = -[Ak2 f (B21C'
2m0
+ C2(Ckt2kv2+ kv2kz2+ kz2kz2])fj
(31.1)
where mo is the free electron mass.

For silicon we have158
2m0 2m0
*A = 4.0 _+ O.l,--B = 1.1 f 0.4,-C = 4.1 f 0.4
h2 fi2 h2
A = 0.04 ev.
The minimum of the conduction band in silicon occurs on the 100 axis, not
on the face. This means that the energy surfaces are six ellipsoids of revo-
lution. If a coordinate system is chosen along the axis of each ellipsoid,
(31.2)
The transverse and longitudinal effective masses are:

! !?! = (0.98 _+ 0.04);- mt = (0.19 f 0.01).
mo mo
The minimum gap between valence and conduction bands, which does
not occur vertically in a band diagram in k space, is 1.14 ev at 0°K. The
minima probably are located about 85% of the way toward the zone
face.160
At the center of the zone, the lowest conduction band level probably
is r16although rzP is not ruled out completely. The (vertical) gap there is
believed to be about 2.5 ev.lS7 A diagram in which the experimental
results and the indications of the latest theoretical calculations are com-
bined is presented in Fig. 15.
The parameters A, B, and C can be related to certain sums of matrix
elements defined by Kittel, through the use of perturbation the0ry.~50.~~l
Let <I"26tzy(0) stand for a state in r26t at the top of the valence band
which transforms as xy. Define:
(31.3a)
B. Lax, F'roc. Intern. Cod. on Current Problems in Cry~talPhys. M.I.T., p. 127,

1957. Rev. Mod. Phys. 80, 122-154 (1958).
169 J. C. Phillips, to be published.
170 JOSEPH CALLAWAY
The sum runs over all the states belonging to r21,the states being
characterized by the index I ; Eo is the energy of I ' 2 6 4 0 ) . Moreover, let
(31.3b)
It may be possible to neglect H2,since the states of symmetry r2&*

are
+12-
+8-
- -
v)
!i4 -
0
> -
z
z
k
0-
0 -
-
W
-I
w-4-
> -
(3
a
w- 8 -
z
w -
-12 -
-16 -
FIG.15. Energy bands in silicon along the 100 and 111 axes according to the
experimental information and the calculations of Woodruff,1" and Baasani.148 Levels
determined by experiment are circled.
high above the valence band. If this is done, F, G, and H I can be deter-
mined from A, B, and C. The results are:
F = -5.0h2/2m, G = -1.1h2/2m, and H I = -3.9h2/2m.
(31.3e)
The results given in the foregoing are different from those given in ref. 151,
where a different choice of sign of the cyclotron resonance constants is
made. Dresselhaus, Kip, and Kittel take the relation B' = - B and
obtain the values
F' = -1.2h2/2m, G' = -0.4h2/2m, Hi = -6.7fi2/2m. (31.3f)
Kane gives some reasons for preferring the choice (31.3e).lK0
Results of the band calculations are only roughly in agreement with
experiment. The early calculations of M ~ l l a n e y land
~ ~ H01mes'~~ using
the cellular method are unsatisfactory because the boundary conditions
were not satisfied adequately. The same appears to be true of the calcula-
tion of Yamaka and Sugita."' In this respect, it should be observed that
the cellular method is rather difficult to apply correctly in the diamond
lattice because the polyhedral cell is complicated.141Jenkins14' has also
applied the cellular method to silicon, using a variational method to
satisfy the boundary conditions. The potential employed in his work and
in the calculations previously mentioned was that constructed by
Mullaney from a self-consistent field. Exchange interactions were not
included. Jenkins obtains reasonable values for the band width a t the
center of the zone, a gap which is somewhat too small, and what is pre-
sumed to be the correct order of levels. Unfortunately, calculations on the
100 axis show that the minimum of the conduction band along that axis
falls below the maximum of the valence band a t the center of the zone;
thus the calculation predicts metallic behavior. This result quite probably
is a consequence of the potential and not a result of the use of incorrect
boundary conditions.
Woodruff has applied the OPW method to ~ i l i c 0 n . He
I ~ ~constructed
a crystal potential using approximate analytical wave functions of the
type developed by Slater assuming a (3~)'(3p)~ configuration. An
exchange interaction was included by means of Slater's free electron
approximation. l2 Analytic approximations to the core eigenfunctions
were found for this potential. Woodruff calculated energies of four states
a t the center of the zone. The convergence of the OPW expansion appears
to be reasonable for all states except rZv.The order of levels obtained by
Woodruff is the same as that shown in Fig. 14. The width of the valence
band at k = 0 was found to be 8.4 ev and the band gap waa 3.6 ev at
k = 0. Bassani has extended Woodruff's calculations to the point X a t
the extremity of the 100 axis.14*The order of levels obtained by Bassani
was used in constructing Fig. 15. The lowest level of the conduction band
a t X is XI, which has an energy rather close to that of rlo. Bassani used
his results and those of Woodruff in combination with the Slater-Koster
tight binding interpolation scheme140 to determine the energy bands
along the 100 axis. The conduction band does have a minimum along
the 100 axis, in agreement with experiment. There is evidence, however,
172 JOSEPH CALLAWAY
from other features of this calculation that the interpolation scheme is

not adequate. The valence band maximum appears to be well out along
the 100 axis and the effective mass at the bottom of the valence band
(rJ is negative.
Phillips has recently constructed an interpolation scheme based on
the OPW methodlSgwhich appears to be more accurate and to require
fewer parameters than the method of Slater and K 0 ~ t e r . The
l ~ ~ Fourier
coefficients of the crystal potential are treated as parameters to be
determined from experimental data or from the results of accurate calcu-
lations a t symmetry points. Phillips has applied this approach to diamond.
silicon, and germanium. Three parameters are used for diamond and
silicon, four for germanium. I n the cases of silicon and germanium the
parameters are determined from experimental results. Spin orbit coupling
is not included. Bands are studied along the 100 and 111 axes. The
results are consistent with all experimental data on these elements. The
superiority of Phillips interpolation scheme over that based on the tight
binding approximation indicates that the electron wave functions most
important for the band structure in these elements are closer to modulated
plane waves than to free atom functions.
The success of semi-empirical techniques such as those of Kane and
Phillips in accounting for a variety of experimental results indicates that
band theory gives a t least good phenomenology. It remains to be seen
whether self-consistent field calculations can yield results in agreement
with experiment. More attention must be given to the choice of the
crystal potential and more elaborate calculations must be performed for
both germanium and silicon.
Brief mention should be made of a short report of an energy band
calculation for silicon carbidelBOin which the tight binding method was
used. The overlapping of first and second neighbors was considered. A
band gap of 6 volts and a band width of 22 volts a t k = 0 were found.
Solutions were obtained along the 100, 110, and 111 axes.
32. GERMANIUM
The experimental information concerning the band structure of
germanium is more detailed than for any other element. Theoretical
studies also have been ~ n d e r t a k e n . ~Many
~ ~ ~of~ the
~ ~experimental
-~~~
papers Iisted in the section on silicon (31) are also concerned with ger-
manium. A few others are listed below. Again no attempt at completeness
160 S. Kobayasi, J . Phys. SOC.Jupun 11, 175 (1956).
161 F. Herman and J. Callaway, Phys. Rev. 89,518 (1953).
162 F. Herman, Physicu 20, 801 (1954).
lo* F. Herman, Phys. Reu. 96, 847 (1954).
is It is convenient to begin by summarizing the experimental
information.
The valence band in germanium has a width of 7.0 volts.166As in
silicon and carbon, the lowest state almost certainly is rl,and the highest
r26,. The spin orbit splitting at the top of the valence band is substan-
tially larger than in silicon, being about 0.29 ev.lS6The energy surfaces
for holes are a set of warped spheres which are characterized by the con-
' ~ ~Eqs. (31.1) and (31.3)].
s t a n t ~ [see
A = 13.1 f 0.4h2/2mo,B = 8.3 f 0.6h2/2mj C = 12.5 f 0.5h2/2m
F = -28.4h2/2mo, G = -1.2h2/2mo, HI = -5.8h2/2mo.
These results imply that there are a band of heavy holes and a band of
light holes.
The minimum of the conduction band occurs'at the center of a hexag-
onal face (point L),16' and presumably corresponds to the state L1. The
energy surfaces for electrons have the form of a set of somewhat needle-
shaped ellipsoids of revolution. The effective masses168(31.2) associated
with them are
2 = 0.0819 f 0.0003
mo
-
mz- 1.64 & 0.03.
mo
The minimum (not vertical) energy gap between valence and conduction
bands is 0.65 ev a t room temperature"' and 0.744 ev at T = 0. The lowest
state at the center of the zone is believed to be rather than r16
r21 because
of the size of F relative to HI described in the foregoing. The vertical
band gap at k = 0 is 0.803 ev at room temperature166 and about 0.88 ev
a t 77OK.lS7The effective mass a t k = 0 in the state normally unoccupied
has been obtained from the oscillatory magnetoabsorption associated
with the direct optical transition,lB6and is m(k = O)/mo = 0.036. It is
inferred from magnetoresistance measurements on germanium-silicon
alloys that the conduction band has six minima along the 100 axis in
germanium as well as silicon. The effective mass ratio - ml is nearly the
mt
same as in silicon namely about 5.1e8The band structure of germanium
is shown, in Fig. 16, in accordance with the best current experimental
and theoretical ideas.
There is considerable experimental information on germanium silicon
164 G. G. Macfarlane and V. Roberts, Phys. Rev. 97, 1714 (1955).
166 B. Abeles and S. Meiboom, Phys. Rev. 96, 31 (1954).
S. Zwerdling, B. Lax, and L. M. Roth, Phys. Rev. 108, 1402 (1957).
167 J. H. Crawford, H. C. Schweinler, and D. K. Stevens, Phys. Rev. 99, 1330 (1955).
188 M. Glicksman and S. M. Christian, Phys. Rev. 104, 1278 (1956).
174 JOSEPH CALLAWAY
Herman has constructed a model which fits the data quite

well, although it is not a rigorous consequence of theory.16aConduction
occurs by migration of electrons in the 111 (L1)minima of the conduction
band in germanium. Although the 100 minima exist, they are too high
above the 111 minima to be populated. As silicon is added, the effective
potential becomes less attractive and the bands tend to rise. In particular,
+6
+4 3
v ) '
3+2.
z
0
+
a 0'
0
W '
J
5-2 a
>.
(3
a L2'
W
z -4
W
-6
FIG.16. Energy bands in germanium along the 100 and 111 axes according to the
experimental information and the calculations of Hermsn.161-16* Spin orbit coupling
is neglected. Levels determined by experiment are circled.
s states rise faster than p states, so that r21 rises faster than and presum-
ably crosses rls.The 111 minima rise faster than the 100 minima. In
the range of composition in which between 8 and 20% silicon is present,
conduction takes place as a result of carriers present in both the 100 and
111 minima. For higher concentrations (20 to 100% Si), only the 100
minima are populated. Thus there is a continuous transition between the
energy bands in germanium and those in silicon. It is no doubt quite
significant for the theory of alloys that these simple ideas seem to be
successful.
The OPW method was applied to germanium in the band calculation
of Herman and Callaway.161A crystal potential was formed from the
169 E. R. Johnston and S. M. Christian, Phys. Rev. 96,560 (1954).
170 G. Dresselhaus, A. F. Kip, H. Y. Ku, and G. Wagoner, Phys. Rev. 100,1218 (1955).
charge distribution obtained from a self-consistent solution for isolated

atoms in the (4~)’(4p)~ state. Exchange effects were not included.
Energy levels were calculated at the point r at the center of the zone and
at the point X a t the center of a square face. Effective masses were found
at the center of the zone. The crucial point L was not investigated. The
width of the valence band was found to be 13.3 volts, and the magnitude
of the gap 1.45 ev. Heavy and light holes were found. The lowest level
in the conduction band at the point k = 0 was predicted to be rlSrather
than r2,.A conduction band minimum along the 100 axis was indicated.
In Herman’s16z subsequent, more elaborate calculation, exchange
interactions were included by selecting an average of two of Slater’s aver-
aging techniques. The core functions were chosen as an orthonormal set
of functions constructed from the Hartree fields. The energies of these
functions, also required in the OPW method, were adapted from x-ray
data. Unfortunately, this procedure is inconsistent with the requirements
of the OPW method, in which the appropriate core wave functions are
eigenfunctions of the crystal Hamiltonian.171 This inconsistency may
spoil the quantitative value of the calculation. This probably is the reason
why some of Herman’s OPW expansions are poorly convergent. Energy
levels were calculated for thirteen nonequivalent k in the zone: r, X g,
W, and L, and certain additional points along symmetry axes (the 100,
111, and 110 axes).
Herman found that the width of the valence band was about 11 volts
and that the minimum, vertical energy gap waa 1.5 volts. The lowest
conduction band state at the center of the zone was FZt, in agreement
with experiment. This was also predicted to be the lowest conduction
band level, which is not in agreement with experiment. Although L1was
found to be the lowest state of the conduction band at the point L, itis
about 1.5 volts above rr.
It is apparent that more detailed calculation will be required before
the extent of quantitative agreement between band theory and experi-
mental results can be determined.
Kane has taken a semiempirical point of view in the analysis of band
structures which seems to be quite fruitful. He has analyzed the shapes
of the bands near the origin in p-type germanium, taking account of the
spin orbit At the center of the zone, in the absence of spin
orbit coupling, the state rw at the top of the valence band is sixfold
degenerate (including spin). Both the spin orbit coupling and the k p -
perturbation remove this degeneracy as one goes away from the center.
The bands away from the center have shapes which differ from the shapes
they would have in the absence of spin orbit coupling. The difference
171 J. Calkway, Phys. Reu. 97, 933 (1955).
176 JOSEPH CALLAWAY
is more radical than a constant factor for the split-off band. Kane con-
structed the secular equation (6.5) using the six constituent functions
belonging to I'w which diagonalize the spin orbit coupling as a basis.
The term k (d X V V ) in the perturbation is neglected since it is quite
small. The constants required are taken from cyclotron resonance experi-
ments. The resulting sixth-order equation factors into two identical
cubics. All bands are doubly degenerate. Kane has solved this cubic
equation along certain axis (100,110,and 111).He finds that the bands
along these lines are not strictly parabolic because of the presence of the
spin orbit coupling. The deviations from parabolic behavior occur in the
range in which the energy from the top of the band is of the order of the
spin orbit splitting of the level. A similar calculation was performed
for silicon. Departures of the bands from parabolic form are also caused
by higher order mixing of valence and conduction band levels. These
effects however, are smaller than the ones included. The probability of
absorption of light by an electron is determined by the matrix elements
of the operator A * p (A is the vector potential). Since the wave functions
at k = 0 in the valence band have a well-defined parity, the interband
transitions that are observed in p-type gerrnaniumlsa depend on the first-
order correction to the wave function brought about by the k * p inter-
action. The transition probabilities can be computed as a function of k
from the cyclotron resonance constants. Kane has done this forger-
manium, and finds fair agreement with experiment.
33. TIN, INDIUM ANTIMONIDE, AND INDIUMAFEENIDE
Tin exist in two forms: a tetragonal form (8) which is stable a t room
temperatures and above, and a cubic form having the diamond lattice
which is stable below room temperature. No calculations of the bands
have been made for either form. Observations of cyclotron resonance
in white tin have been reported by Fawcett and by Kip et ~ 1 . " Values ~
of the effective mass ranging from 0.23 mo to 0.43 mo were reported by
Fawcett, and a range from 0.2 to 3 mo was noted by Kip. A spread of
effective masses is to be expected for a complicated crystal structure.
Gray tin is a semiconductor having a very small band gap, namely
about 0.08 ev. It would be an interesting element to study extensively;
however, the difficulty of obtaining single crystals has discouraged
measurements. The effective mass should be quite small, of the order of
0.01 or less, if the band structure is similar to that of indium antimonide,
which is probably the case.
Indium antimonide is of considerable interest because of its small
171 E. Fawcett, Phys. Rev. 103, 1582 (1956); A. F. Kip, D. N. Langenberg, B. Rosen-
blum, and G. Wagoner, Phys. Rev. 108, 494 (1957).
energy gap (0.23 ev at 0°K) and high electron mobility. KO calculation
of the band structure has been made from first principles. Considerable
experimental information exists, and a semiempirical analysis of the band
structure has been made.17aThe symmetry properties of the structure
and their implications for the energy bands have been a n a l y ~ e d . ~A~ . * ~
few of the experimental papers are listed below. 174-178 The experimental
situation is not as clear for InSb as it is for Gel but the model proposed
by Kane17aseems to be well established.
I n order to understand the calculations and experiments concerning
the 111-V compounds, a brief discussion of the results of a study of the
symmetry properties is in order. The principal differences between the
symmetry properties associated with energy bands in the diamond struc-
ture and in the zincblende structure result from the lack of inversion
symmetry of the latter. From Kramer’s theorem, one still has the rela-
tion E(k) = E ( - k ) ; however, a twofold degeneracy of spin states
throughout the Brillouin zone is not required. It is worth noting that the
spin orbit coupling plays a very vital role in InSb particularly, in con-
sequence of the high atomic number of the atoms involved. As a result
of the existence of the spin orbit interaction in the perturbing Hamil-
tonian for the cell periodic functions, it is not necessary that all the bands
be flat a t k = 0. In particular, representations formed from I’s, which is
situated a t the top of the valence band, will not have zero slope.
The width of the valence band in InSb is not known. The maximum
of the band apparently occurs in the vicinity of the center of the zone.
The linear terms give a maximum in the valence band away from k = 0
in the 111 direction. Kane estimates that this maximum has an energy
about ev above the energy at k = 0, and is located about 0.3% of
the distance to the zone edge. There is evidence that both heavy holes
and Iight holes exist; however, the form of the energy surfaces is not
known as well as in germanium and silicon. The average effective masses
are about 0.18 mofor the heavy holes and 0.04 mo for the light holes.
The conduction band is centered at k = 0. The energy surfaces are
spherical, and are characterized by an effective mass equal to 0.013 mi.
As a result of the very small gap, it is not likely that this curvature is
maintained away from k = 0. The small effective mass implies that the
178 E. 0. Kane, J . Phys. Chem. Soh& 1, 249 (1956).

174 G. Dresselhaus, A. F. Kip, C. Kittel, and G. Wagoner, Phys. Rev. 98,556 (1955).
175 H. Y. Fan and G . W. Gobeli, Bull. Am. Phys. SOC.6, 298 (1956).
176 V. Fbberts and J. E. Quarrington, J . Electronics 1, 152 (1955).
177 H. J. Hmstowski, F. J. Morin, T. H. Geballe, and G. H. Wheatley, Phys. Rev. 100,
1672 (1955).
179 E. Burstein and G. S. Pious, Phys. Rev. 106, 1123 (1947).
178 JOSEPH CALLAWAY
density of states in the conduction band is quite low. Consequently the

conduction band becomes filled quite readily and the conduction elec-
trons soon become degenerate. There is evidence for an increase in the
effective mass with increasing energy, that is, as the conduction band is
filled. I n third order of k, the conduction band is split into two singly
degenerate bands except along the 100 and 111 directions. This splitting
has not yet been observed.
The semiempirical analysis of K ~ n e ' ?resembles
~ his earlier work on
germanium and silicon.'$*In this case, the interactions of the conduction
band, the two valence bands which are degenerate at k = 0, and the
split-off valence band which occurs as a result of the k - p and the k-inde-
pendent spin-orbit coupling interactions are treated exactly. The interac-
tions with other bands can be treated as perturbations. The bands are
parabolic at k = 0 in this approximation. The terms linear in k originate
-
in the k (d X VV) interaction and in combinations of the k p and the -
k-independent spin orbit interactions. The matrix element of k * p
between conduction and valence bands can be derived from the effective
mass for electrons determined by cyclotron resonance with reasonable
accuracy, since it is likely that this interaction dominates as a result of
the small gap. Kane finds:
P s = - I <r6lpJreZ>12
h2
= 0.44 (in atomic units).
m2
The k independent spin orbit splitting is estimated to be 0.9 ev.

The matrix element P determines the probability of the fundamental
optical transition between valence and conduction bands at k = 0. The
wave functions for values of k leaving the center can be found to a good
approximation as the eigenvectors of the Hamiltonian matrix diagonalized
previously. This makes it possible to calculate the absorption constant
associated with direct transitions in the vicinity of k = 0. The results
agree fairly well with the experiments of Fan and G0be1i.l~~
The compound indium arsenide has also been the subject of some
experimental study. Lax has found an energy gap 0.360 f 0.002 ev at
room temperature. The effective mass of electrons is about 0.03 mo.
This probably implies that the conduction band minimum is at the center
of the zone.
Stern and T a l l e ~ have
' ~ ~ observed the room temperature infrared
absorption in p-type indium arsenide, and have carried out an analysis
of this absorption which is similar to the work of Kane on indium anti-
~ valence band maximum is assumed to be at the center
m ~ n i d e . " The
179 F. Stern and R. M. Talley, Phys. Rev. 108, 158 (1957).

of the zone.'*O From the analysis, the k-independent spin orbit splitting
is estimated to be 0.46 ev and the mean heavy hole mass is 0.4 ma. Light
holes, whose effective mass would be of the order of the electron mass,
should also exist.
34. GALLIUM AFSENIDE
The labor involved in an accurate band calculation is so large that it is
scarcely feasible to make self-consistent calculations for all substances
of interest. For this reason, it is desirable to develop perturbation pro-
cedures which will make it possible to relate the bands in several mate-
rials. The 111-V and 11-VI semiconductors are particularly interesting.
They crystallize in the zincblende structure, which is the binary analog
of the diamond lattice consisting of two interpenetrating face-centered
cubic lattices. Thus the Brillouin zones are the same as for the group IV
elements just considered. Furthermore, the lattice constants in a hori-
zontal sequence, that is, compounds formed of elements lying in the same
row of the periodic table, are nearly equal. Herrnanls1 has made a general
survey of horizontal sequences and diagonal sequences of these com-
pounds. The latter are formed of elements in different rows of the periodic
table. He finds that the increase in the energy gap within a sequence as
the atoms become more unlike can be accounted for approximately by
perturbation theory. In the case of a horizontal sequence, the principal
perturbating potential is antisymmetric with respect to the midpoint
of the line joining the two atoms in the unit cell. Consequently, the
principal effects occur in second-order perturbation theory. The change
in the energy gap between GaAs and ZnSe is three or four times that
between GaAs and Ge, which is about what one would expect from
simple reasoning.
Callaway has considered this perturbation technique in more detail
for gallium arsenide182in an effort to relate the energy bands in that
substance to those in germanium. A perturbating potential was calcu-
lated from the self-consistent fields for neutral atoms of gallium, germa-
nium, and arsenic, and was supplemented by introduction of approximate
experimental effective charges on the atoms. The potential was expressed
as the sum of symmetric and antisymmetric parts centered about the
18% As in the case of indium antimonide, there should be a linear term in E(k) near
k = 0 which will displace the maximum slightly from k = 0. This linear term may
be somewhat more important in InAs than InSb because of the greater difference
in atomic number between the constituents. Stern and Talley believe the linear
term will markedly affect the shape of the absorption a t low temperature.
181 F. Herman, J. Electronics 1, 103 (1955).
18) J. Callaway, J. Electronics 2, 330 (1957).
180 JOSEPH CALLAWAY
midpoint of the lines joining the neighboring gallium and arsenic atoms.
The antisymmetric part appears to be considerably the larger. The
effects of the antisymmetric perturbing potentials can be studied quali-
tatively by determining from symmetry arguments which matrix ele-
ments exist. Combined with an order of magnitude estimate of the size
of the matrix elements and reasonable guesses concerning the energy
denominators, the displacement of the levels under the influence of the
perturbation can be determined. The essential results are as follows.
There is a general tendency for the valence band to move to lower energies
relative to germanium whereas the levels at the bottom of the conduction
band are relatively stationary. The minimum of the conduction band
probably shifts from the point L at the center of a hexagonal face to the
center of the zone. An increase in the optical energy gap of the observed
order of magnitude is found. There is experimental evidence to indicate
that the effective mass in gallium arsenide is small, about 0.04 mo, and
of the order of that reported for the r2l band in germanium.lS8 This
suggests that the conduction band minimum is indeed at the center of
the zone.
V. The Transition Metals
35. GENERALCONSIDERATIONS
Under the title of transition metals, we will consider only those
elements of the fourth period of the periodic table in which the free
atoms possess incomplete d shelIs. It is convenient to add copper to this
list, since there have been several attempts to draw inferences concerning
the bands in the transition metals proper from calculations of energy
bands in copper. The transition metals are particularly interesting
because of their magnetic properties. Iron, cobalt, and nickel are ferro-
magnetic; chromium and manganese are antiferromagnetic. Many of
the simple compounds of these elements are antiferromagnetic. The
magnetic properties are naturally ascribed to the d electrons, and it then
becomes a pqncipal task of band theory to give a satisfactory quantum-
mechanical amount of these properties.
Detailed discussions of the band theory of ferromagnetism and anti-
ferromagnetism can be found in papers by Slater.2J84.186 This is not the
place for a thorough account of these theories. It will suffice to state that
it has not been possible to give a quantitative explanation of the existence
of the origin of either ferromagnetism or antiferrornagnetism on the band
I** L. Barcus, A. Perlmutter, and J. Callaway, Bull. Am. Phys. SOC.[2] 3, 30 (1958).
184 J. C. Slater, Revs. Modern Phys. 26, 199 (1952).
186 J. C. Slster, Phys. Rev. 82, 538 (1951).
picture. Some of the difficulties involved should become apparent in the

course of this discussion.
Experimental evidence, particularly on the magnetic behavior (atomic
moments) of these elements and their alloys, suggests a rather smooth
and gradual variation of electronic structure from element to element,
regardless of rather substantial changes in crystal forms. Thus it seems
reasonable to try to construct a general model of the d bands in the
transition elements; there have been several attempts at t h i ~ . ' 8 ~ ~The
*0
earliest proposal was that of Mott. The basic ideas of Mottlg6were that
there is a narrow d band of width less than 1ev which is overlapped by a
wide 4s band. A narrow d band is necessary in the band theory of ferro-
magnetism so that the decrease in energy arising from increased exchange
upon spin alignment will outweigh the increase in energy resulting from
promotion of the electrons to higher band states. The magnetic properties
are determined by the d band while the cohesion and the conductivity
are produced by a relatively small number of s electrons, less than one
per atom. Scattering of s electrons into vacant d band levels, where the
density of states is high, accounts for the relatively large resistivity.
On the other hand, Pauling assumes that the d electron (two in iron)
responsible for the magnetic properties form a band of essentially zero
width.189 The atomic model is adequate for these electrons. The other
electrons, s and d in the free atom, form a very broad band based on
hybridization of s,p, and d orbitals. Ferromagnetism is believed to be pro-
duced by the exchange coupling of the atomic d electrons with the con-
duction band, in a manner similar to the proposal of Zener.191 A small
number of the conduction electrons contribute to the net magnetic
moment.
A function giving the density of states which was calculated by
Slater1g2-1g4 has been used for the interpretation of a number of experi-
ments on the properties of the transition elements. Slater derived this
function from a calculation of the energy bands in copper made previously
by K r ~ t t e r Characteristic
.~~~ features of the Slater curve are the high
density of states a t the bottom and top of the band and a minimum near
the middle of the band. Slater used this density of states to estimate the
188 N. F. Mott, Proc. Phys. SOC.(London) 47, 571 (1935).
187 N. F. Mott, Proc. Phys. SOC.(London) A62, 416 (1949).
ISSL. Pauliig, Phys. Rev. 64, 899 (1938).
189L. Pauling, Proc. NuU. Acad. Sci. U.S.39, 551 (1953).
1ooF. Bader, K. Ganzhorn, and U. Dehlinger, 2.Physik 137, 190 (1954).
191 C. Zener and R. R. Heikes, Revs. Modem Phys. 26, 191 (1953).
199 J. C. Slater, Phys. Rev. 49, 537 (1936).
19) H. M.Kmtter, Phg8. Rev. 48,664 (1935).
194 E. Rudberg and J. C. Slater, Phys. Reu. 60, 160 (1936).
182 JOSEPH CALLAWAY
Curie temperature of nickel, but it has been applied to the entire series
of transition elements. It is therefore worth emphasizing here that the
errors in the basic band calculation resulting from faulty application
of the cellular method are so serious that the density of states derived
from it has little validity. For example, the fivefold degeneracy of the
d bands was not removed at the center of the zone, and this leads to a
quite spurious peak in the density of states a t the bottom of the band.
Rudberg and Slater extended the calculated density of states to higher
energies in a study of the inelastic scattering of electrons by c0pper.1~4
Quantitative calculations of the energy bands in the transition metals
are unusually difficult. The problem of attaining self-consistency is
present in a very aggravated form. Not only is it more difficult to obtain
self-consistency than in the other systems, but the consequences of a
lack of self-consistency are more serious. There may be a large number of
d electrons present on each atom. An appropriate charge distribution
must be assumed from them. There are two basic difficulties: (1) A uni-
form distribution will, very probably, be far from self-consistent, (2) It is
known from calculations of wave functions in free atoms that the wave
functions and energies of d electrons are rather sensitive to small changes
in the potential. Adequate self-consistent field calculations for free atoms
of these elements do not exist. In addition, if application is made to the
ferromagnetism problem, self-consistency must also be achieved with
respect to the number of electrons of each spin present.
Recent d band calculations have not been sufficiently quantitative to
lead to a precise theoretical model. However, a number of comments can
be made which are reasonably well-founded theoretically, and which
point the way to something more sophisticated than the models of Mott,
Pauling, and Slater. The extent to which experimental evidence supports
these ideas is not completely clear.
I n agreement with the early work of Mott, the d band is quite narrow,
but not as narrow as he proposed. It would seem that the band width
must be greater than 1.5 ev. A figure of about 3 ev seems reasonable. The
shape of this band should be in substantial agreement with the normal
level order for an isolated d band in the appropriate lattice. In particular
there is little evidence for a split of the d band into bonding and anti-
bonding sub-bands as proposed by Bader et al.lgoThe d electrons must
be assumed to contribute substantially t o the cohesive energy. The 4p
levels appear to lie relatively well above the 3d band so that mixing of p
and d levels should not be too important.
The band model outlined above is in a sense a synthesis of the results
of band calculations which have been performed. Recently Mott and
Stevens1s4ahave constructed a model of the d bands in the transition
metals according to which there is a very significant difference between
the nature of the bands in the closed-packed and in the body-centered
transition metals. In the latter, Mott and Stevens propose that the
d band is split into two parts, one formed from functions of I'26' sym-
metry and associated with rather diffuse wave functions, and the other
part formed from functions of r12symmetry with compact wave func-
tions. The conventional band structure obtains in the closed-packed
metals. In chromium, the r12 band is believed to be above the Fermi
surface and is unoccupied; in iron, it contains the two electrons per atom
which are responsible for the magnetic properties. Electrons in this band
contribute nothing to the conductivity. The conduction electrons are in
the r2v band. This model is based on interpretation of experimental data
for these metals; in particular, the measurements of R. J. Weiss on x-ray
scattering which are discussed in subsequent sections. It is not consistent
with existing band calculations or with the normal level order in the
body-centered cubic lattice.
A few remarks should be made concerning the general applicability
of the energy band picture to the d electrons in the transition elements,
particularly in regard to the question of ferromagnetism. It is well known
that the energy band theory erroneously predicts ferromagnetism in the
limit of infinite atomic separation. This is a result of the fact that the
energy band theory overestimates the energy of the nonmagnetic state
in this limit: polar states of the individual atoms in which some have too
many or too few electrons are predicted in large number. The energy of
the ferromagnetic state does go to the correct limit as the atomic distance
becomes large because the Pauli principle effectively prevents such polar
states. The trouble is an aspect of the general problem of treating the
electron interaction in more detail than is possible in the Hartree-Fock
approximation. The basic difficulty facing the energy band theory in the
application to actual ferromagnetic metals is this: if the band is narrow,
the neglect of correlations leads to a serious overestimate of the tendency
to ferromagnetism; if the band is wide, the promotion energy inhibits
ferromagnetism. It is difficult to arrive at a quantitative estimate of the
error induced by the neglect of correlations. Van Vleck has proposed
abandoning the standard band theory in favor of a generalization of the
Heisenberg model in which there is a nonintegral number of spins per
atom, and the spins are constantly being redistributed among the lattice
He finds that this model may give a lower energy. Callaway has
1940 N. F. Mott and K. W. H. Stevens, Phil. Mag. [S] 2, 1364 (1957).
106 J. H. Van Vleck, Revs. Modern Phys. 25, 220 (1957).
184 JOSEPH CALLAWAY
made a crude estimate of the effects of correlation in opposing ferromag-

netism for iron a t the observed lattice spacing1gswith the result that the
tendency toward ferromagnetism calculated by energy band theory
should be reduced by about 0.25 ev. A self-consistent energy band cal-
culation for d electrons is required for further progress.
36. EXPERIMENTAL INFORMATION
Experimental information pertaining to energy bands in the transition
metals is far less precise and detailed than in the case of semiconductors.
Much of the existing material pertains to the density of states.
Measurements of the low-temperature specific heats of the transition
elements have been analyzed by Horowitz and and by Daunt.1vB
The electronic specific heat is directly proportional to the density of
states on the Fermi surface. Horowitz and Daunt interpret the data in
terms of a common density of states for all the transition elements.
There is no fundamental justification for such a procedure, but if it is
accepted, a pronounced minimum is indicated a t the position of the
Fermi surface in chromium, a maximum in the vicinity of vanadium, and
a strong maximum toward the end of the series. A high peak may exist
in manganese.
The temperature variation of the magnetic susceptibility of the para-
magnetic transition elements has been discussed by Kreissman and
~ ~ value of the magnetic susceptibility is proportional to the
C ~ d l e n . ’The
average value of the density of states N ( E ) in an interval of a few kT in
width centered a t the Fermi energy. The temperature variation of the
susceptibility depends on the first and second derivatives of the density
of states, and is usually negative. A positive temperature coefficient can
be obtained in the vicinity of a minimum. The data then indicate that
the Fermi energy in titanium and chromium comes near a minimum in
the density of states.
It may be useful to comment in regard to the proposed interpretation
of these properties that it is quite legitimate to regard the data as indi-
cating that the density of states in chromium a t the Fermi energy is
much smaller than in nickel, for example, a t its Fermi energy, and prob-
ably that the Fermi energy in chromium is near a minimum of its density
of states. It requires much more faith in the simplicity of d bands than
m J. Callaway, PbD. Thesis, Princeton University, 1955 (unpublished).
19’ M. Horowitz and J. G. Daunt, Phys. Rev. 91, 1099 (1953).
lBsJ. G. Daunt in “Progress in Low Temperature Physics” (C. J. Gorter, ed.),
Vol. 1, p. 202. Interscience, New York, 1955.
1~ C. J. Kreissman and H. B. Callen, Phys. Rev. 94, 837 (1954).
experience justifies to believe that the density of states of nickel will show
a minimum at a position corresponding to the Fermi level in chromium.
The soft x-ray emission spectra of the transition elements have been
studied by a number of worker^.^^^-^*^ The emission intensity is propor-
tional to the product of the transition probability and the density of
states. The observed emission cannot be interpreted directly in terms
of a density of states unless particular assumptions about the transition
probabilities are made. A determination of the total band width should
be more reliable. Both 4s and 3d electrons may contribute to the observed
emission, but it is likely that the d electrons will dominate because they
are present in greater number. Unfortunately there are serious disagree-
ments between the results of the various authors, and further work, both
experimental and theoretical, would seem to be required. According to
the results of Skinner,202the observed band widths are in the vicinity of
6 ev for all the transition metals, but are apparently somewhat greater for
chromium, vanadium, and copper than for the others. The band widths
reported by Gyorgy and Harvey are in reasonable agreement with those
of Skinner except in the case of iron where a smaller band width of
3.7 f 1.0 ev204was reported. Any interpretation of the results in terms
of a density of states would be premature, except that it may be noted
that there is no indication of detailed structure.
Beeman and Friedman have attempted an interpretation of the struc-
ture beyond the K absorption edge especially in copper and nicke1206in
terms of the density of states calculated by Rudberg and Slater.lg4
Measurements of the Hall effect in the transition elements indicate
that conduction occurs predominantly by means of holes in vanadium,
chromium, manganese, and iron; by electrons in cobalt and n i ~ k e l . ~ ~ ~ * ~ O '
Since it is unlikely, although not impossible, to find holes in an s band,
it is probable that carriers in the d band dominate the conduction process
in those elements where hole conduction is observed. The effective masses
of carriers in the d band should be substantially higher than of those in
the s band, so if there were any appreciable number of s electrons avail-
able, the latter would have the predominant effect. One concludes that
the number of effective s electrons is quite small.
J. Farineau, Ann. phys. 10, 20 (1938).
901 Y. Cauchois, Phit. Mug. [7] 44, 173 (1953).
zo* H. W. B. Skinner, T. G. Bullen, and J. E. Johnston,Phil. Mug.[7] 40,1070 (1954).
*oa E. M. Gyargy and G. G. Harvey, Phys. Rev. 87, 861 (1952).
204 E. M. Gy6rgy and G. G. Harvey, Phys. Rev. 95,365 (1954).
)06 W. W. Beeman and H. Friedman, Phys. Rev. 06,392 (1939).
S. Foner and E. M. Pugh, Phy8. Rev. 91,20 (1953).
107 S. Foner, Phys. Rev. 107, 1513 (1957).
186 JOSEPH CALLAWAY
Weiss has recently presented measurements on the form factors for

x-ray scattering which challenge the generally accepted concepts of the
d band in the transition metals in a very serious way.2o8The observed
intensity of a Bragg reflection depends on a form factor which is the
appropriate Fourier coefficient of the charge density. The form factor is
rather difficult t o determine experimentally since corrections must be
made to allow for extinction. An experimental form factor can be com-
pared with theory if electron wave functions are available. In computing
the form factors, Weiss used wave functions based on a self-consistent field
(with exchange) for the core electrons. The remaining charge distribu-
tion required to account for the results is a measure of the number of d
electrons. The 4s electrons will not contribute to the form factor, since
it is not sensitive to a uniform charge distribution. It is assumed that the
distribution of d electrons is rather compact. Weiss’ results for the num-
ber of d electrons are as follows:
Chromium 0.2 & 0.4 Nickel 9.5 & 0.3
Iron 2 . 3 & 0.3 Copper 9.8 f 0.3
Cobalt 8.4 & 0.3
The discrepancy between the results for the body-centered elements,

chromium and iron, and the rest which have close-packed structures is
not accounted for by any theory. If these results are verified there is
apparently a serious disagreement between theory and experiment
(see Section 39 for further discussion).
We now begin a detailed consideration of individual band calculations.
37. TITANIUM
The energy bands in titanium have been studied by Schiff.209,210 Both
the hexagonal and the body-centered cubic forms were investigated. A
rough semiempirical potential was found by the method of P r o k o f j e ~ ~ ~
to represent the Ti+4ion. The potential of a uniform distribution of three
valence electrons was added to this. Only the states at the center of the
zone were investigated for the hexagonal form. Later an error was dis-
covered in some of the expansions and the corresponding boundary
conditions employed for the hexagonal case.
For the body-centered form, the energies of five states at the points
r and H were found using the cellular method and the boundary condi-
208 R. J. We& and J. De Marco, Rev. Mod. Phys. SO, 59 (1958).
209 B.Schiff, Proc. Phys. Soc. (London)A68, 686 (1955).
*lo B. Schiff, Proe. Phys. Soc. (London)A69, 185 (1956);see also S.L. Altmann, Proc.
Phys. 8oc. ondo don) A69, 184 (1956).
tions of Howarth and Jones.71 The principal results of this calculation
are that the r12d state at the center of the zone lies above the lowest
s state I’l, the H12d state a t the zone corner is lower than r12as is required
by the normal form of the energy bands in the body-centered lattice, and
that one of the lowest p band states, Hl5, lies quite well above the d
states investigated.
Recently Altmann and Cohan have reinvestigated the states a t the
center of the zone in hexagonal titanium.210aThe cellular method was
applied. The calculation was made possible by the development of a
computer program for the least squares fitting of boundary conditions.210b
Calculations were made for each of three potentials: (a) the potential
obtained by SchitT,***(b) a potential obtained from a self-consistent
field with exchange for Ti+4to which was added the potential of a uniform
distribution of three electrons, and (c) the same Ti+* potential as in (b),
but with the valence electrons in atomic orbitals for a 3d24s configuration.
The most accurate calculations employed potential (a). Eight spherical
harmonics were employed in the expansion of the wave function, and
boundary conditions were applied a t sixteen point on the surface of the
polyhedron. The energies of twelve representations were obtained. The
Iowest states were found to be, in order of increasing energy (Herring’s
notationes) rl+,rr-,r5+,r6+,and r6-.These states are predominantly s
and d states with the s state lowest. The latter three states are doubly
degenerate. Comparison of the results obtained with the different poten-
tials showed that the relative position of the four lowest levels in (a) and
(b) agreed to within 0.06 rydberg, but that the results of (c) were in
serious disagreement with those of (a) and (b). Thus, the sensitivity of the
d electron states to the distribution of valence electrons is emphasized.
Altmann has also applied the cellular method to a calculation of
energy levels at the center of the zone in zirconium. The calculation is
similar to that previously discussed for titanium. The potential was
obtained from a self-consistent field for Zr+4. The potential of the con-
duction electrons was assumed to be that of a uniform charge distribution.
The order of the levels is the same as found for titanium. There are four
mainly d states above the ground state, which is s-like.
38. CHROMIUM
No detailed calculations of energy bands in chromium have been
published. However, Slater and Koster have applied a tight binding
interpolation scheme to this element. They have taken values for the
required two center potential integrals from the calculations of Fletcher
210aS. L. Altmann and N . V . Cohan, Prac. Phys. Sac. (London) 71, 383 (1958).
*lo* S.L. Altmann, Proc. Roy. Sac. (London) A244, 141, 153 (1958).
188 JOSEPH CALLAWAY
and Wohlfarth for nickel.211.212 The distance between nearest neighbor

atoms differs by only 0.25% in chromium and nickel at 20°C. Slater and
Koster set up the matrix components of energy for the body-centered
cubic lattice, inserted the parameters (first neighbor interactions only
and neglecting orthogonality corrections) and solved the resulting fifth-
order determinantal equation at many points through the Brillouin zone.
From these results they computed a density of states by numerical
methods. Sufficient care was taken to insure that the density of states
would be an accurate expression of the calculated band structure. It is
asserted to be characteristic of the body-centered cubic transition metals.
Unfortunately, the underlying assumptions are not adequate. The cal-
culated density of states turns out to be symmetric about its midpoint.
This is so only in consequence of the small number (three) parameters
used in the tight binding approximation. This symmetry definitely
would be removed in a more precise calculation. Moreover, the energy
bands determined by Slater and Koster disagree very seriously with the
normal form of energy bands in the body-centered lattice. They predict,
for instance that the separation of the d bands at the center of the zone
is about the same as it is at the corner H . Also they find that HW lies
below r12.There are other discrepancies as well. It is probable that these
results are a consequence of the unjustified use of the parameters deter-
mined by an inadequate calculation for nickel for another element.
Slater and Koster proceed to discuss the antiferromagnetism of
chromium in terms of this model of the band structure. Chromium is
believed, as the result of neutron diffraction, to be weakly antiferro-
magnetic.218 Atoms on each of the two interpenetrating simple cubic
lattices presumably have oppositely-directed moments. It is necessary
to use a cubic cell containing two atoms in a band calculation for such a
system. The Brillouin zone is now a simple cube which has half the volume
of the ordinary zone for the body-centered lattice. The potential energy
of an electron of upward spin is different on the two atoms in the unit
cell. In the simple tight binding approximation employed, such a differ-
ence in potential energy would tend to produce a gap in the d bands,
coming at the middle of the density of states. As the d band is presumably
half full (see, however, ref. 208), the density of states at the Fermi level
would be quite low, being determined by the overlapping s band. This
model is consistent with the experimental evidence. Slater believes that
such a model would also be self-consistent theoretically. It is not clear
211 G. C. Fletcher and E. P. Wohlfarth, Phil. Mag. [?I 42, 106 (1951).
*I* G. C. Fletcher, Ptoc. PhyS. Soc. (Lmrdon) A66, 192 (1952).
*I* C. G. Shull and M. F. Wilkinson, Reus. Modern Phys. 26, 100 (1953).
ELECTRON ENERGY BAND8 IN SOLIDS 189
to this author just how much of this viewpoint can be maintained in view
of the inadequate band calculation.
39. IRON
There have been several calculations of energy bands in ir0n.~14-~18
The cellular calculations of Manning214for body-centered iron and of
Greene and Manning for face-centered2I5iron have the defect of inade-
quate satisfaction of the boundary conditions, in common with most
early band studies. This work can hardly be said to be of quantitative
value.
Callaway has made a study of energy bands in bcc iron using the
method of orthogonalized plane waves, and has applied the results to a
calculation of the tendency to ferromagnetism. 216 The original potential
was taken from a self-consistent field without exchange for the free iron
atom. A configuration d6s2 for an iron atom waS assumed to exist in the
solid initially. Exchange interactions were included on the basis of $later’s
free electron approximation12 at first. Subsequently, a correction to this
was calculated from the Hartree-Fock equations. The results showed
that the initial potential was not self-consistent in the sense that the
d band was predicted to be quite far below the s band. Thus a configura-
tion d8s0was predicted in place of the d6s2 assumed.
This result is of some interest in view of the experiment of Weiss208
concerning the effective number of d electrons in iron. Although no band
calculations have been made on the basis of a crystal potential which
is consistent with the work of Weiss, it would appear that a charge dis-
tribution substantially more uniform than of atomic iron cannot be self-
consistent. If the charge distribution conforms to the Weiss model, the
+
potential at reasonable distances from a nucleus (from to 8 of the dis-
tance to the atomic cell boundary) will be substantially more attractive
than in the free atom because of the reduced screening. This kind of
attractive potential will tend to bind the d electrons quite strongly and
should result in a d band which is well below all the s-p levels. These d
functions will be even more tightly bound than the atomic functions.
Consequently, if the results of Weiss are correct, a fundamental dis-
agreement between theory and experiment apparently exists.
On the basis of Callaway’s calculation, the shape of the d band con-
a14 M. F. Manning, Phys. Rw. 88, 190 (1943).
116 J. B. Greene and M. F. Manning, Phys. Rev. 88, 203 (1943).
316 J. Callaway, Phys. R w . 99, 500 (1955).
*nF. Stem,Ph.D. Thesis, Princeton University, 1955 (unpublished).
M.$&%yneki, Ac& phy.9. P o h . 14, 493 (1955); 15, 111 (1956).
190 JOSEPH CALLAWAY
forms fairly well to the normal order of levels for the body-centered
lattice. In particular the separation of the d band levels at the center of
the zone is much less than at the corners and faces of the zone. The
width of the d band is approximately 2 ev. I n view of the fact that the
assumed potential probably binds the d electrons too strongly, the cal-
culated band width should be regarded as a lower limit. The order of the
levels at r, H,and N is shown in Fig. 17.
-.550
-
m.600
a
a
W
m
P
&650
Y
>
0
a
W
2300
W
t750
~ H
FIG 17. Level diagram for iron according to Callaway.*l6The N 1levels were
obtained using an interpolation scheme and are less reliably placed.
A lower limit on the band width is of interest in connection with

Zener’s theory of the origin of ferromagneti~m.~~~Zener described the 4s
electrons in the transition elements by band wave functions and the 3d
electrons by localized atomic functions. He assumed that there is one
4s electron per atom. He calculated the decrease in energy obtained by
aligning the spin of the d shells and reversing the spins of some of the
conduction electrons so as to be parallel to the d electrons. Thus ferro-
magnetism is assumed to arises from the s-d exchange coupling. The
decrease in energy upon alignment is estimated to be about 0.05 ev per
atom in iron if the direct exchange interaction between the d shells on
adjacent atoms is neglected. One difficulty with this theory is that the
finite width of the d band is neglected. With a band about 2 volts wide,
110 C. Zener, P h p . Rev. 81, 440 (1951);83, 299 (1951).
the increase in the Fermi kinetic energy is far too large to permit the
exchange coupling between the s-d electrons to cause ferromagnetism by
itself. The promotion energy was estimated to be about 0.7 ev per atom
on the basis of the narrow band obtained in the work of ref. 216.
A crystal potential calculated on the basis of a d7s configuration was
also investigated. The difference between this potential, having exchange
integrals calculated from the Hartree-Fock equations, and the one used
previously was computed and treated by first-order perturbation theory.
The bottom of the s band was found to be below the d band, so that the
calculation is more nearly self-consistent. The splitting of the d and
s bands when the spin of one d electron per atom was reversed in order
to produce a magnetic state was computed using two sets of d band wave
functions. The splitting was found to be between 2.46 and 3.16 ev for
the d band. The tendency to ferromagnetism was calculated to be be-
tween 0.89 and 0.54 ev per atom. This result, which is much too large,
confirms the view that the calculated band width is too small.
The low 4p level H16was found to lie quite far (about 0.7 ry) above
the d hand. This result suggests that 4p functions do not play an impor-
tant role in the band structure.
Suffczynski has calculated the two-center potential integrals for
iron218in the tight binding approximation, using wave functions with
exchange and a simple screened Coulomb form for the potential. First
and second nearest neighbors were considered. The overlap integrals of
wave functions on different atoms were not calculated. The band struc-
ture implied by these integrals has not been computed in detail.
Stern has attempted a computation of the cohesive energy of iron.*17
His method is a modification of the tight binding approximation. A pre-
liminary calculation using wave functions and potentials based on the
configuration dss2 gave results in agreement with those of Callaway for
this configuration: namely a very narrow d band which lies entirely
below the 4s band. Stern then calculated self-consistent wave functions
without exchange for higher configurations of atomic iron: d7s1and d8.220
The energy of the 3d electrons is raised quite substantially in going
from the des2 configuration to the d7s1and ds configurations. The eigen-
values are -0.79 ry, -0.50 ry, and -0.34 ry, respectively. The wave
functions become more diffuse in the higher energy configurations; such
functions yield wider bands. A calculation based on wave functions from
the d8 configuration gave a band width of about 0.5ry, which is probably
too large, and placed the bottom of the 4s level below the 3d band. Stern
believes that an approximately self-consistent configuration in the solid
would be d7Js0.8.The order of levels calculated by Stern for the 3d band
**O F. Stern, Phys. Rev. 104,684 (1956).
192 JOSEPH CALLAWAY
is in good agreement with the normal order for the body-centered-cubic

lattice.
Evidence concerning the wave functions of magnetically active elec-
trons in iron comes from experiments on the polarization of slow neutrons.
These experiments have been interpreted by Steinberger and Wick.221
The experiments involve the standard form factor for the distribution of
magnetically active electrons. This form factor was calculated by Stein-
berger and Wick on the basis of a d7s1 configuration. Exchange integrals
from the Hartree-Fock equations were included. Although the boundary
conditions used are not appropriate for d electron wave functions in
solids, the results indicate that the wave function for these electrons
must be rather more compact than those given by the Hartree field with-
out exchange for the free atom. The d electron wave function obtained
by Callaway also exhibits this compactness.
The alignment of the 3d electrons tends to polarize the 4s band
through the s-d exchange coupling. The amount. of this polarization has
been calculated by Callaway216and by Pratt.222Callaway obtained a
magnetization of the s band of 0.07 P B per atom, and Pratt, by a more
detailed calculation, found about 0.2 C(B per atom. The difference is
principally a result of the larger number of s electrons (one per atom)
assumed by Pratt. It is worth remarking that recent work, which explains
the negligible polarization of the s band in dilute Cu-Mn
does not require that this polarization be absent in a ferromagnetic
metal in which long-range magnetic order prevails. A substantial screen-
ing of the s-d exchange interaction does not seem to be required either.
40. NICKEL
The energy bands in nickel have been studied by Slater192 and by
Fletcher and Wohlfarth.211.212 Slater obtained a density of states for nickel
from Krutter's calculation for copper,lgaas has been discussed in Section
35. He proceeded to estimate the tendency to ferromagnetism of nickel.
He obtained empirical values for the appropriate exchange integrals
from an analysis of the atomic spectra. This work led to a value of 0.99 ev
per atom for the decrease in energy as a result of the increased exchange
when spins are aligned. This result is lower than the value ranging from
1.23 to 1.58 ev obtained for iron in the work of ref. 216. The difference
originates in the use of a different method of averaging the exchange
interactions and of slightly different values for the appropriate integrals.
Slater calculated the tendency to ferromagnetism and obtained reasonable
1%' J. Steinberger and G. C. Wick, Phys. Rev. 76, 994 (1949).
*** G. Pratt, Phys. Rev. 106, 53 (1957).
*** J. Owen, M.Browne, W. D. Knight, and C. Kittel, Phys. Rev. 102, 1501 (1956).
ss4E. W. Hart, Phys. Rev. 106, 467 (1957).
116 K . Yosida, Phys. Reu. 106, 893 (1957).
agreement with the observed Curie temperature. It is likely, however,
that this good agreement is related to use of too great a band width,
and that a more accurate calculation would give a larger tendency to
f erromagnetism.
The tight binding calculations of Fletcherz1*were made with the use
of wave functions for the Cu+ ion. The potential was taken as a simple
screened Coulomb interaction. Potential integrals were calculated with
first neighbors only. Overlap integrals involving wave functions on differ-
ent atoms were not included. The band width obtained was 2.7 ev. A
curve giving the density of states was computed graphically for the upper
part of the band and good agreement with experiment was obtained for
the electronic specific heat. It is interesting that the computed band width
is about half that used by Slater.lgaFletcher has not classified the bands
according to the notation of Bouckaert et at.,Is but it can be deduced
from the degeneracies and from the compatibility relations that the
results are in reasonable agreement with the normal level order for the
face-centered cubic lattice. In particular, the separation of the d levels
at the center of the zone is considerably less than on the faces of thezone.
The calcuhtion of Fletcher cannot be regarded to be quantitative.
The particularly serious approximations are the neglect of mixing of
s and d bands, the use of the screened Coulomb potential, and the
neglect of overlap and second-neighbor potential integrals. The neglect
of s-d mixing may lead to erroneous band shapes.
Koster used the integrals caIculated by Fletcher to determine
numerically a density of states for nickel which covers the entire band.22s
Energy levels were found at 680 points within one forty-eighth of the
Brillouin zone. The density of states is, no doubt, an accurate representa-
tion of the Fletcher-Wohlfarth band structure. The over-all accuracy
depends on the validity of the original calculation, which is somewhat
in doubt. It is interesting that the density of states shows the charac-
teristic dip which is approximately in the middle of the band, discussed
in Section 35.
41. COPPER
There have been several studies of energy levels in ~opper.19***~~-288
The cohesive energy of copper has been calculated by F u ~ h s * ~and 7 by
G. F. Roster, Phy8. Rw. 98, 901 (1955).
K.Fuche, Proc. Roy. Soc. (Landon)A l l l , 585 (1935); AlSS, 622 (1936).
*** M.I. Chodorow, Phys. Rev. 66, 675 (1939).
r)o S. R. Tibbs, Proc. Cambridge Phil. Soc. 84, 89 (1938).
*so D. J. Howarth, Proc. Roy. Soc. (London)A220, 513 (1953).
)*IK. Kambe, Phy8. Rev. 99, 419 (1955).
*s2D. J . Howarth, Phy8. Rev. 99,469 (1955).
la*M. E’ukuehi, Prop. Themet. Phys. (Kyoto) 16,222 (1956).
194 JOSEPH CALLAWAY
Kambe.2a1The early calculation of Fuchs employed the cellular method

in a manner quite analogous to the original calculation of Wigner and
Seitz for sodium’? except that the potential was taken from a self-
consistent field suplemented by an exchange interaction. The effective
mass was assumed to be unity, and the interactions of the valence elec-
trons were neglected. In order to obtain reasonable values for the com-
pressibility, Fuchs found it necessary to take account of the repulsive
energy between the ions, which he estimated by a statistical method.
In this way he obtained a cohesive energy of 34 kcal/mole and a lattice
constant of 4.2 A in comparison with the experimental values of 81 kcal/
mole and 3.6 A.
Kambe used the quantum defect method4? to calculate the cohesive
energy of copper. Because the atomic cell is small, the potential in
the vicinity of a cell boundary is not completely hydrogenic. Correc-
tions for departure of the potential from the simple Coulomb form at the
cell boundary were made on the basis of a self-consistent field. The
quantum defects were somewhat more difficult to extrapolate than in the
case of the alkali metals because of the presence of configuration interac-
tion in the atomic spectra. Neglecting the interactions between the
ions, Kambe obtained a cohesive energy of 62.4 kcal/mole at the ob-
served lattice spacing.234The effective mass at the bottom of the band
is m/mo = 1/Ez = 1.01. A part of the discrepancy between theory and
experiment in regard to the cohesive energy may be associated with the
neglect of k4 terms in the Fermi energy, but most is probably the result
of rather strong van der Waals attractions between the ions.66.236 These
interactions contribute perhaps 25 kcal/mole to the cohesive energy.
Their strength can be related to the optical absorption. The short-range
exchange repulsion of the ions is also important, particularly in the
calculation of the lattice constant and the compressibility. There should
also be a correction for the Coulomb interaction with the conduction
electrons of the slightly interpenetrating d shells.236
Howarth’s two calculations are concerned with the 3d band and higher
levels in the conduction band.230.2a2 The first calculation employed the
cellular method. Boundary conditions were determined and satisfied in
much the same way as in the work of Howarth and Jones.’’ The second
calculation employed the augmented plane wave method of Saff ern and
Slater.2a7Two potentials were used for the conduction band in each
284 Kambe’s published result has been modified by using the corrected form of Wigner’s
correlation formula. The correction amounts to 3.1 kcal/mole.
285 J. Friedel, Proc. Phys. SOC.(London)BBS, 769 (1952).
2a6 Y . C. Hsu, Phys. Rat. 89, 975 (1951).
237 M. M.Saffern and J. C. Slater, Phys. Rat. 92, 1126 (1953).
calculation: One was based on a self-consistent field in which exchange

was excluded and the other on a self-consistent field which included
exchange. Exchange interactions between valence and core electrons were
not taken into account. The contribution of one 4s electron was added to
the potential in calculating the 3d band whereas that of one 3d electron
was subtracted. In using the augmented plane wave method, it is neces-
sary to assume that the potential is constant outside an inscribed sphere.
The results of the cellular method and the augmented plane wave cal-
culation differ very substantially. For example, the order of the levels
a t the center of the zone is reversed. It is improbable that all the differ-
ence can be ascribed to the assumption that the potential is constant
outside the inscribed sphere. Since the order of levels in the d band
obtained from the cellular calculation agrees quite well with the normal
order in the face-centered lattice, whereas the results obtained from the
augmented plane wave treatment differ violently, it seems likely that a
mistake exists somewhere in the latter. In consequence, only the results
of the cellular calculation will be reported.
TABLEXIII. EIGENVALUESOF THE d BANDFOR COPPERACCORDING
TO
HOWARTA (IN RYDBERGS) CELLULARCALCULATION
Xs -0.344 Xs -0.13
L1 -0.248 XI -0.12
rls* -0.235 Xs -0.088
rl, -0.195
TABLEXIV. EIGENVALUES BANDFOR COPPER

OF THE CONDUCTION
(IN RYDBERGS)
Howarth*s" Fukuchi
rl -0.596 -1.282
L$ 0.18 -0.696
XI, 0.20 -0.499
L1 0.055 -0.393
KI -0.344, -0.260
XI 0.24 -0.108
The d band eigenvalues are given in Table XIII.2aoThe width of the

d band is 3.46 ev. In Table XIV, the results for the conduction band of
copper are given both in accordance with the Hartree-Fock potential
~ O as computed by Fukuchi.2aaThe results are
used by H o ~ a r t h , ~and
valid for the observed lattice constant. Since different potentials were
used in Howarth's calculation for the s and d bands, a separate calculai-
tion is required to relate the eigenvalues. The result 'placecthe top of
196 JOSEPH CALLAWAY
the 3d band 3.7 ev below the Fermi level in the 4s band (the latter is
7.1 ev above the bottom of the 4s band). The bottom of the d band ( X , )
is 0.1 ev below the bottom of the 4s band (rl).
Fukuchi has made an OPW calculation of the conduction band of
copper."* His potential differs from the Hartree-Fock potential used by
Howarth by the addition of an exchange interaction obtained with the
use of Slater's free electron average12and of the contribution of a uniform
charge density of conduction electrons. It is not clear that Fukuchi found
the appropriate core functions for this potential. It is also not clear that
enough plane waves were included to obtain convergence for all the
states. The effective mass appears to be rather less than 1; however, the
question of convergence is important here.
Mott has proposed that states at the top of the first Brillouin zone in
copper are ~-1ike.6~ This is suggested by the optical properties (the color
presumably is a result of transitions between the 3d band and the conduc-
tion band), and by the x-ray emission spectrum. The states a t the bottom
of the second Brillouin zone would then be s-like. This conjecture is
supported by the calculation of Fukuchi, but not by that of Howarth.
The effective mass on the Fermi surface in copper has been determined
to be m/mo = 1.45 from optical measurements by Schulz.2as Since the
effective mass at the bottom of the band is very close to 1.0, the result
suggests that substantial negative k4 terms are present in E(k). The
situation is somewhat similar to that prevailing in the alkali metals. The
electronic specific heat of copper has also been me&sured.2aB The effective
mass determined from these measurements is 1.38, in reasonable agree-
ment with the optical results.
Pippard has made a detailed study of the anomalous skin effect in
single crystals of copper and has constructed a model of the Fermi surface
which agrees with his The surface constructed differs
from spherical in that it is extended in the direction of L (refer to Fig. 2) ;
is depressed a bit at K where the curvature is anisotropic and almost
zero along the line KL;has a rudimentary ridge along the line XL with a
saddle point where the curvature becomes slightly concave. The surface
is approximately described by the equation.
kz2 + ku2 + kz2 - akz2kV2kz2
+ b(kz2ku2+ kU2kz2+ kz2kz2) = 1
with constants a = 5.6, b = 0.3. It is probable that the surface touches
the zone face a t L. The electron specific heat calculated with this model
*** L. G. Schulz, Advancea in Phys. 6, 101 (1957).
*uW. S. Corak, M. P. Garfunkel, C. B. Satterthwaite, and A. Wexler, Phys. Rev. 98,
1699 (1955). Read&are given in terms of an effective mass by Schdz.*a*
*40 A. B. pippard, Phil. Tram. Roy. Soc. AIM), 325 (1957).
ELECTRON ENERGY BANDS IN SOLiDd i97
of the Fermi surface is characterized by a thermal effective mass 1.87,
which is significantly larger than the experimental result.2agIt is possible
that the discrepancy could be removed by a correlation correction to the
density of states as suggested by Pines.*6Further indications of significant
deviations of the Fermi surface from spherical form originate in measure-
ments of the specific heat of a-brasses a t low temperatures.241Rayne
noted a rapid variation in y, the coefficient of the linear term in the low-
temperature specific heat, with the concentration of zinc at low concen-
trations. The sharp initial rise is not consistent with a parabolic form for
the density of states in copper. The measurements of Rayne can be
interpreted qualitatively in terms of a crude model of the density of
states in copper proposed by Jones.242The approach of the Fermi sur-
face to the boundary of the Brillouin zone in the vicinity of the point L
causes a sharp increase of the density of states in the vicinity of one s elec-
tron per atom, which is then followed by a linear decrease. The thermo-
electric power of the noble metals can also be explained in terms of this
model.24aHowever, no indication of a maximum in the curve for the
density of states just beyond the Fermi surface for copper have been re-
vealed from measurements of the magnetic susceptibilities of a-bras~es.~'~
VI. Other Substances
42. SILVER AND GOLD

The cohesive energies of silver and gold have been studied recently
by Kambe.lal These metals have the face-centered cubic structure. The
quantum defect method was employed in the calculation, as in the case
of copper (Section 41). The corrections for departures of the potential
from a simple Coulomb form near the cell boundary were determined
from the results for copper, and may be somewhat less accurate. For
silver and gold, Kambe obtained a cohesive energy of 59.0 and 52.2 kcall
mole respectively at the observed lattice constant (r, = 2.99 in each
case). The experimental values are 68.0 and 92.0 kcal/mole. The cal-
culated effective masses a t the bottom of the bands are 0.992 and 0.994,
respectively. The principal discrepancies between theory and experiment
are presumably due to the van der Waals attractions of the ions, but the
other corrections mentioned in Section 41 may also be important.
Tibbs has calculated energy bands in copper and ~ilver.~~VAs in other
241 J. A. Rayne, Phy8. Rev. 108, 22 (1957).

242 H. Jones, Proc. Phys. Soc. (London)49,250 (1937).
*aH. Jones, PYOC. phy8. Soc. (London)AM,1191 (1955).
244 W. G. Henry and J. L. Rogers, Phil. Mug. [S] 1, 237 (1956).
198 JOSEPH CALLAWAY
early cellular method calculations, the boundary conditions are satisfied

so inadequately that the results are not quantitative.
Effective masses of electrons on the Fermi surface have been deter-
mined by optical absorptionz3* and thermal measurements (electron
specific heat). The results are given in Table XV.
TABLEXV
Metal Optical m/mo Thermal m/mo
Ag 0.97 0.96
AU 0.98 1.16
The discrepancy between the optical and thermal effective masses for
gold is probably outside the experimental error. If true, it implies a
rather warped Fermi surface. The agreement between the results for
silver and that computed for the bottom of the band may possibly imply
absence of k4 terms in the band structure, but this seems somewhat
unlikely in view of indications that such terms are important in copper
and gold.
There would seem to be an opportunity here for more detailed band
calculations to determine whether the Fermi surface is distorted from
spherical symmetry and whether it actually does touch the Brillouin
zone. In the absence of self-consistent fields with exchange for free atoms
of silver and gold, the quantum defect method could be extended t o the
higher states. Further theoretical studies are important because these
metals are easy to work with experimentally.
43. TUNGSTEN
Energy bands in metallic tungsten (bcc) have been studied by Man-
ning and C h o d o r ~ wThe
. ~ ~calculation
~ involved the cellular method and
was based on a potential derived from a self-consistent field. The same
comment applies to this calculation as to many other prewar cellular
method calculations : the boundary conditions are satisfied sufficiently
inadequately that the results have no quantitative value. The shape of
the d band and the density of states are probably quite erroneous. The
cohesive energy of tungsten has been studied by HsuZa6on the basis of
Zener’s theories.21g
44. BISMUTH
Bismuth has a rhombohedra1 structure. The structure is perhaps
thought of most easily as a distorted simple cubic lattice. A simple cubic
146 M. F. Manning and M. I. Chodorow, Phys. Rar. 66,787 (1939).
lattice is composed of two interpenetrating face-centered cubic struc-
tures. If one of the component face-centered lattices is displaced with
the atoms moving away from their normal places, the bismuth structure
is produced. Since the free atom contains five electrons, the Brillouin
zone shown in Fig. 18, which holds five electrons per atom, is often
It is not the smallest possible zone: the reduced zone resembles that for
the face-centered cubic lattice, Fig. 2, quite closely except that it is
skewed somewhat, the three A axes being not quite perpendi~ular.~~7
f /
/
I
A.
7
FIQ.18. Brillouin zone for bismuth according to Jones.246 This zone can contain
five electrons per atom. Overlapping occurs across the faces of the zone.
Bismuth is a semimetal. The bands can be separated into valence and

conduction bands which overlap very slightly. As in the case of graphite,
small numbers of electrons and holes will be present at absolute zero.
No detailed calculation of energy bands in bismuth has been made.
Morita considered the bands in the tight binding approximation
including only nearest neighbor potential integrals and neglecting overlap
integrals. 247
S. Mase also applied the tight binding approximation to
His work differs from that of Morita in that spin orbit coupling is
included. Mase constructed character tables for the double group of
H. Jones, Proc. Roy. SOC.(London) A141, 396 (1934).
A. Morita, Sci. Repts. TBhku Univ. First Ser. 38, 144 (1949).
t470 s. Maw,J . Phys. SOC.(Japan) 13, 434 (1958).
200 JOSEPH CALLAWAY
bismuth. He considers bismuth to be in the configuration s2pa,and includes

only the p electrons. The two-center approximation is made and nearest
neighbors alone are included. With these approximations, a quantitative
calculation is impossible, but qualitative aspects may be correct. The
slight overlapping of the bands containing small numbers of free elec-
trons and holes characterized by small effective masses can be regarded
as due to the removal of degeneracies which would be present in a cubic
structure. The effect of this rhombohedra1 distortion is small compared
to the spin-orbit coupling. The interesting points are those corresponding
to L in the Brillouin zone of the face-centered cubic structure. In bismuth,
however, not all these points are equivalent. There are two types: (A
and C in the notation of Mase). Levels at these points will be slightly
displaced with respect to each other: also, there is a small splitting of
levels a t these points which would otherwise be degenerate. These ideas
may also be applicable t o antimony and arsenic.
A large amount of experimental information has accumulated on
energy bands in bismuth. Measurements of the De Haas-van Alphen
effect, cyclotron resonance, and galvanomagnetic effects can be inter-
preted in terms of a simple model of the energy surfaces originally pro-
posed by S h ~ e n b e r gA. ~few
~ ~ papers are listed belo~.249-~5”
Aubrey and Chambers interpret the data in the following way.268a
The electrons occupy three ellipsoids in k space. If k, and k, are chosen
along the binary and trigonal axes, one ellipsoid can be represented as
E = alkr2 + u2kw2+ aYkz2+ 2a4k,ks.

The two other ellipsoids can be obtained by rotations through %/3 about
the trigonal axis. The coefficients ai are: a1 = 168, uz = 2.0, = 100,
u4 = - 10. Referred to the principal axes, the effective masses are 0.0060,
0.330, and 0.0101. Holes occupy a single ellipsoid:
where bl = 0.71 and ba = 0.19. The overlap between the bands of holes
and electrons is EI = 0.0184 ev. The Fermi level is at Ep = 0.017, ev
848 D. Shoenberg, Proc. Roy. Soc. (Lon&on)A170,341 (1939).
249 V. Heine, Proc. Phys. Soc. (London)A69,513 (1956).
*so B. Abeles and 8. Meiboom, Phys. Rev. 101, 544 (1956).
*I* M. Tinkham, Phye. Rev. 101,902 (1956).
161 B. Lax,K.J. Button, H. J. Zeiger, and L. M. Roth, Phys. Rev. 102, 715 (1956).
*I* J. S. Dhillon and D. Shoenberg, Phil. Tram. Roy. Soc. A248, 1 (1955).
*ma J. &. Aubrey and R. 4 Chambers, J . Phyu. C h m . SoZidu 8, 128 (1957).
ELECTRON ENERQY BANDS I N SOLIDS 201
a t 4°K.At that temperature there are 0.86 X hole or electron per
atom present. The ratio of the density of states for electrons to that of
holes is 1 :27.
45. SELENIUM AND TELLURIUM
Selenium and tellurium are semiconductors with unusual crystal

structure. A spiral chain which runs along the c axis of the crystal is
located at the center and each of the six corners of a hexagon. The inter-
atbmic spacing along a chain is much smaller than the separation between
chains. Each atom forms covalent bands with its two neighbors in the
chain; the chains are probably held together by van der Waals forces.
The bond angle in a chain is close to 90" (actually somewhat larger).
Studies of energy bands in these elements have been made by Callen264
and by Reitz.2ss Callen replaced the actual hexagonal structure by a
related tetragonal structure with simpler symmetry properties. Reitz
asserts, however, that this model will yield metallic conductivity. A
group theoretical analysis of the actual selenium structure has been
given by Asendorf.266
Reitz constructed a model in which only the atoms along a single
chain are considered, somewhat analogous to the layer model of graphite.
He has applied the tight binding approximation, including only nearest
neighbor potential integrals with atoms along the chain. The band struc-
ture is given in terms of these integrals as undetermined parameters
[ ( p p )and (ppu) in the notation of Slater and K ~ s t e r l ~Overlap
~]. integrals
of wave functions on different atoms are ignored. Spin orbit coupling is
neglected. This approximation may be quite inappropriate for tellurium.
As a first approximation, a model in which the bond angle is 90" was
studied. In this simple model, the bands are triply degenerate. Increasing
the bond angle removes the degeneracy. The p bands split into three
groups separated by gaps, the lower two being occupied normally. The d
bands were also considered. Matrix elements for optical transitions were
determined. The absorption limit for direct transactions at long wave-
lengths occurs at k, = u/c and depends on the polarization of the light
parallel or perpendicular to the c axis of the crystal. From the order of
the levels, it is predicted that the absorption edge for light polarized
perpendicularly to the c axis is at longer wavelength (independently of
whether the transitions are p-p or p-d), in agreement with experiments
for tellurium.2b1Increasing the bond angle decreases the energy gap.
*64 H.B. Callen, J . C h . Phy8. 22, 518 (1954).
166 J. R. Reite, Phys. Rev. 106, 1233 (1957).
166 R. H.Aaendorf, J . C h . Phys. 27, 11 (1957).
157 J. J. Loferski, Phys. Rev. BS, 707 (1954).
202 JOSEPH CALLAWAY
Since such a decrease occurs in tellurium, the results are capable of

explaining the change in the band gap under pressure. It is quite likely,
of course, that more elaborate calculations will be required to interpret
experiments in a quantitative way.
The optical band gaps reported by LoferskizS7are 0.32 ev for light
polarized perpendicularly to the c axis, and 0.37 ev for parallel polarized
light. The transmission beyond the edge also depends on the state of
polarization.
Choyke and Patrick have measured the absorption of light in sele-
nium.268They find a n energy gap of 1.79 k 0.01 ev at room temperature
and a large decrease (9 X 15-4 ev/”K) of the gap with temperature. They
also interpret the absorption near the edge as the result of indirect
transitions, which is not predicted in the calculation of Reitz.266
46. ALKALIHALIDES:SODIUM
CHLORIDE
The alkali halides have been studied intensively for many years.
The information pertaining to energy bands in these substances is, how-
ever, relatively meager. Much attention has been given to the problems
of determining the nature of classes of imperfections in these crystals,
and to understanding the effects of the strong coupling between electrons
and the vibrating lattice. Such subjects are, however, outside the scope
of this review.
The binding energy of the alkali halides is principally a result of the
electrostatic interaction of the ions. A reasonably satisfactory account
of this energy can be given on the basis of a simple semiclassical theory
which is described in standard texts. Quantum-mechanical treatments
of the cohesive energies have been given by Landshoff 259 and Liiwdin.260
The calculations of Lowdin are the most recent and will be discussed
briefly here. Since the individual ions have closed shells, the Heitler-
London and Bloch wave functions are equivalent except for normaliza-
tion.261 No attempt is made to calculate the energy bands. The cohesive
energy is derived by calculating the expectation value of the Hamiltonian
relative to the theoretical energies of the ions in the Hartree-Fock
approximation. Lijwdin determined the correction to the atomic wave
functions so that functions on different atoms are orthogonal. The
cohesive energy can be broken into three parts: the electrostatic energy
268 W. J. Choyke and L. Patrick, Phys. Rev. 108, 25 (1957).

269 R.Landshoff, 2.Phyaik 102, 201 (1936); Phys. Rev. 62, 246 (1937).
280 P. 0. LGwdin, Arkiu Mat. Astron. Fysik SbA, Nos. 9, 30 (1947); see also Advuncea
in Phys. 6, 1 (1956).
261 See F. Seitz, “The Modern Theory of Solids,” p. 301. McGraw-Hill, New York,
1940.
of the undistorted charge distribution, the exchange energy of the
undistorted wave functions, and the S-energy, which contains all the
effects of distortion of the wave functions through overlap. The latter
contribution gives rise to the repulsive energy between the ions, which
could not be treated from first principles in the classical theory. Only the
interaction between nearest neighbors is considered,
Wave functions were obtained from self-consistent fields including
exchange. Inclusion of exchange in treating the ionic wave functions is
important because the functions which do not include exchange are too
diffuse, and therefore lead to an overestimate of the repulsive energy.
The agreement between theory and experiment is quite good, especially
for NaCl. The calculated cohesive energy and lattice parameters for the
substance are 183.2 kcal/mole and 5.50 A; the empirical values are
182.8 kcal/moIe and 5.58 A, respectively. The agreement with experiment
generally is good for the chlorides LiCl and KCL; the agreement is
reasonable for the fluorides LiF and NaF, but is not quite so close. There
seems to be a general tendency for the theoretical calculations to over-
estimate the compressibility.
There have been some calculations of energy bands in NaC1.262-264
The calculations of Shockley and Casella are concerned with the
highest filled bands which are formed from the 3p wave functions on
the C1- ions. Shock1ey26*chose a crystal potential in the following way.
An effective charge distribution was taken from a self-consistent field
without exchange for C1- which was normalized so that all eight valence
electrons were contained in a sphere whose volume is equal to the differ-
ence between the volume of the unit cell in NaCl and the volume of a
spherical Na+ ion. The potential of seven such electrons produces the
field acting on any one. The field of a Na+ ion was assumed to be the
same as that in sodium metal. A constant potential (the Madelung
potential) was added to represent the fact that the lattice is not neutral.
In addition, the potential on a sodium ion was modified by allowing one
electron to move off into the six surrounding chlorine ions. Various
methods of applying the boundary conditions were investigated. None
of the methods used is likely to be very accurate much aa in the case of
many of the early calculations using the cellular method. The band form
appears to be in agreement with the normal level order in the face-
centered cubic lattice if boundary conditions are satisfied under condi-
tions in which the sodium atoms are neglected entirely, or if both sodium
and chlorine atoms are included in the boundary conditions. The band
*(* W. Shockley, Phys. Rev. 60, 754 (1936).
S. R. Tibbs, Trans. Faraday SOC.56, 1471 (1939).
Is4R. C. Gasella, Phys. Rev. 104, 1260 (1956).
204 JOSEPH CALLAWAY
width in the latter, more accurate, case is about four volts. This is likely
to be an overestimate because exchange was not included and the wave
functions are, in consequence, too diffuse.
C a ~ e l l has
a~~ estimated
~ the minimum width of the Cl- 3p band, using
the tight binding approximation. The sodium atoms were neglected.
Wave functions were taken from a self-consistent field with exchange
for neutral argon. Such wave functions are likely to be too compact,
X
FIG.19. Qualitative sketch of the chlorine 3 p band in NaCl according to Shock-
ley:*(*and Casella.*"
because of the greater atomic number, so that the band width obtained
should be a lower limit. The ionic potential was also taken from the self-
consistent field. Exchange was added with the use of Slater's free electron
approximation.12 This method should lead to an overestimate of the
binding and to a lower limit for the band width. Potential integrals
which included only nearest neighboring chlorine atoms were considered.
Overlap integrals were neglected. The band width was found to be about
1 ev; the computed bands agree with the normal level order. The width
is estimated to be accurate within 30%. The qualitative form of the
bands scheme agrees with that of Shockley and is probably correct. It is
illustrated in Fig. 19.
Tibbs tried to estimate the effective mass of the electrons in the con-
duction band in sodium chloride.260 Proceeding in a way similar to

Shockley, he calculated conduction band levels at I’ and X. From the
difference of these, he obtained a band width and an effective mass close
to unity. The validity of this calculation is open to criticism on several
grounds. Any comparison with experiment would have to include the
effect of the interaction between electrons and lattice vibrations.
47. POTASSIUM
CHLORIDE
Liiwdin and Howland have studied the lattice energy and energy
bands in potassium ~hloride.266,~66 Howland’s calculation of the lattice
energy is similar to that of Lijwdin260except that the interactions between
nearest neighboring chlorine ions, which are second neighbors in the
lattice, were included. The result of including the second neighboring
chlorine ions is to increase the repulsion due to overlap substantially,
so that the cohesive energy is lower than that of Liiwdin, but is in reason-
able agreement with experiment. The overlap energy amounts to about
15% of the cohesive energy. The lattice energy calculated by Howland
is slightly too high, that is, the binding is too small. The discrepancy is
ascribed to correlation between electrons on different ions.
In the band calculation, an eighth-order secular equation containing
the interaction between 3 s and 3P levels on both the potassium and
chlorine ions was solved. Chlorine-chlorine overlap and potential integrals
were included as mentioned above. Energy values were obtained for
twenty-two independent values of k. The 3 p band of chlorine has a
width of 1.52 electron volts. This is considerably lower than the result
obtained by Shockley for NaCl, but is in reasonable agreement with the
lower limit obtained by Casella. The lower bands are narrower and well
separated.
Measurements of the K x-ray absorption and the soft x-ray emission
have been reported and discussed by Parratt and There
are several possible interpretations of these experiments, but it seems
quite likely that the chlorine 3P band is much narrower than the 4 ev
obtained by Shockley for NaCl. The band width would seem to be in
the vicinity of 1 or 2 ev, in reasonable agreement with the calculations
of C i ~ e l l aand
~ ~ Ho~land.~66
~ The gap between valence and conduc-
tion bands is estimated to be about 9.5 ev on the basis of ultraviolet
absorption.26R
ZssL. P.Howland, Phys. Rat. 109, 1927 (1958).
966L. G. Parratt and E. L. Jossem, Phys. Rat. 97, 916 (1955).
167 L. G. Parratt and E. L. Jossem, J . Phys. Chem. Solids 2, 67 (1957).
*(* N. F. Mott and R. W. Gunney, “Electronic Processes in Ionic Crystals.” Oxford
University Press, London & New York, 1948, quoted by Parratt and Jossem.*6@
206 JOSEPH CALLAWAY
AND LITHIUMFLUORIDE
48. LITHIUMHYDRIDE
The cohesive energies of these (fcc) crystals have been studied by
Lowdin and L ~ n d q v i s t ~ 6according
~ . * ~ ~ to the procedures mentioned in
Section 46. The agreement with experiment is quite reasonable, but there
are unsettled theoretical problems regarding LiH. Further information
may be found in the review by Lowdin.2uoA calculation has recently been
made by Morita and T a k a h a ~ h i . ~ ~ ~ ~
Ewing and Seitz have calculated energy bands in these sub~tances.~~O
A form of self-consistency was obtained with respect to the states at the
center of the zone. The calculations were continued until the charge
distribution of the valence electrons computed from the wave functions
of occupied states at the center of the zone was the same as that used in
computing them. The distribution of the 1s electrons in the fluorine ion
was taken from a self-consistent field without exchange. The ionic poten-
tial previously computed by Seitz4I was used for lithium. Correction for
the Madelung potential was made in a way depending on the charge in
each cell. Exchange interactions were not included in these calculations.
The wave equation was solved with the aid of the cellular method.
Unlike many other cellular method calculations of the prewar period,
proper account was taken of crystal symmetry in the choice of spherical
harmonics for the expansion of the wave function and in the satisfaction
of boundary conditions. It is not entirely clear that enough of the proper
terms were included in the expansion of the wave function to satisfy all
the boundary conditions satisfactory. Later work has indicated that
quite high 1 values may be required and has shown a strong dependence
of the energy on the points chosen for the application of the boundary
conditions. However, the calculation was far in advance of others of
that time.
Energy values in LiF were found for fifteen symmetry types at
r, X, L, K, and the midpoint of the 100 axis A. The bands are qualita-
tively similar to those shown in Fig. 19 for NaCl, except that the 2s
valence band and the conduction band also were studied. The results
are in reasonable, although not perfect, agreement with the normal
order of levels for the face-centered lattice. Some of the eigenvalues for
LiF are given in Table XVI. According to the criterion of self-consistency
used, it was found that the lithium, fluorine, and hydrogen atoms are
only very weakly ionic in contradiction t o the classical picture. This
result might be altered somewhat if exchange and correlation effects
*m S. 0. Lundqvist, Arkiu Fysik 8, 177 (1954).
*6Qa A. Morita and K. Takahashi, Progr. Theoret. Phys. (Kyoto) 19, 257 (1958).
370 D. H. Ewing and F. Seitz, Phys. Rev. 60, 760 (1936).
were included, or if a more completely self-consistent calculation were

carried out. The principal reason for the small effective charge probably
is that cells of equal volume were taken for the two ions. The charges
would be given more properly if the cell volumes were determined from
the ionic radii. The highest valence band (LiF) was found to have a width
of about 5 ev. The valence band maximum occurs at the point K; and
the (vertical) gap between valence and conduction bands is about 7 ev.
TABLEXVI. ENERGY
LEVELSIN LIF
s-like states
rl = -0.77,0.7
LI -0.76, 0.82
XI = -0.73
K I = -0.68. 0.01 (contains TI aa well)
plike states
X I = -0.11
L2 0.03
KI = 0.05
x
4 = 0.10
La = 0.12
rls= 0.18
Kc = 0.27
In lithium hydride, the valence band is found to have a width of about

2.5 ev whereas the energy gap is about 6 ev. Experimental values of the
energy gaps quoted by Ewing and Seitz are 10 ev and 6.5 ev in LiF and
LiH, respectively.
49. LEADSULFIDE
A rather elaborate calculation of energy levels in lead sulfide (fcc)
has been made.271A crystal potential was constructed from self-consistent
fields for the core electrons of sulfur and lead. These were obtained by
scaling the Hartree fields for Ar, C1,and Hg. As in the case treated by
Ewing and S e i t ~ , *self-consistency
'~ with respect to the charge distribu-
tion of occupied valence band states at k = 0 was achieved in this cal-
culation. The 6s and 6 p electrons of Pb and the 3 p electrons of S (eight
in all) were included in the self-consistent field calculation. An appro-
priate correction w a ~added for the constant part of the Madelung
potential.
The cellular method was applied. The appropriate Kubic harmonics
were obtained for the expansion of wave functions. Considerable care
D. G. Bell, D. M. Hum, L. Pincherle, D. W. Sciams,and P. M. Woodward, Ptoc.
Rag. Soe. (London) A217, 71 (1953).
208 JOSEPH CALLAWAY
was taken so that the matching of boundary conditions would be free

from arbitrariness. Errors in the empty lattice test were of the order of
2% for states of high symmetry. A method involving matching of Fourier
coefficients was used for calculation of E(k) curves. Terms up to I = 3
were included in the expansion of the wave function for all states, and
higher 1 values were included for states at k = 0.
The self-consistent procedure mentioned above leads to an effective
ionic charge of 1.4. This figure was obtained under the assumption that
the distribution of charge of the states at k = 0 is representative of the
entire zone. It was found, however, that the charge distribution depends
significantly on k.
Energy levels were calculated at the center of the zone and along the
100 and 110 axis. The 111 axis was not considered. From the states cal-
culated, PbS was found to be a semiconductor with a minimum energy
gap (not vertical) of 0.3 ev and a minimum vertical gap of 1.3 ev. The
maximum of the valence band was found to occur along the 110 axis
about 39 of the distance to the face, and the minimum of the conduction
band at the point K on the face (state KI). Calculations of the bands
which define the gap were carried out for a smaller lattice constant, but
with the same potential, in order to estimate the change in the gap with
temperature. The result was equivalent to a shift of +2 X ev/deg.
The experimental situation in regard to PbS is somewhat obscure,
and much work remains to be done. Indirect transitions have been
observed in the infrared absorption with an energy gap of 0.37 ev; direct
transitions have a gap of 0.41 ev.272
50. ZINC SULFIDE
Zinc sulfide exhibits two crystal forms: zincblende (which is face-
centered cubic) and wurtzite (hexagonal). There are two interesting
studies of energy levels in zinc sulfide, both of which emphasize the cubic
form.273-274Asano and Tomishima calculated the cohesive energy of zinc
sulfide according to the method developed by Schmidlas for diamond.
No attempt was made t o determine the energy bands. Two electron
functions are defined, each of which contains two parts. One part repre-
sents the ionic state in which both the 4s electrons of zinc have been
transferred to the sulfur, and the other part represents a covalent state
in which both the zinc and the sulfur atom are in s'pa states. An arbitrary
constant A is induced giving the ratio of the amplitudes of the covalent
W. W.Scadon, Phys. Reu. 109, 47 (1958).
S. Asano and Y. Tomishima, J . Phys. Soc. Japan 11,044 (1956).
274 J. Birman, Phys. Rev. 109, 810 (1958); C. Shakin and J. Birman, Zbid. 109, 818
(1958).
to the atomic state. The energy of the crystal is calculated as a function

of the parameter A , which is varied to minimize the energy. The wave
functions for sulfur and the 4P functions for zinc were obtained by inter-
polation from SCF calculations for C1- and As+, respectively.
The minimum of the energy occurs for A = 0.22 and gives a cohesive
energy of 2.92 rydbergs per ion pair. This can be compared with the
experimental result of 2.72 rydbergs per ion pair. The effective charge
was determined from the parameter A to be f1.66 for zinc and sulfur,
respectively.
Birman studied in detail the problems involved in the calculation of a
crystal potential for use in a band calculation for ZnS.274He discussed
the problem of the effective charge to be assumed and concluded that
charges of f0.5 for zinc and sulfur are most reasonable. The crystal
potential is expressed as the sum of three parts: (1) The spherically
symmetric Coulomb potential of the charge distribution within the
equivalent volume sphere; (2) the potential within one cell due to the
other ions in the crystal; and (3) the exchange potential, computed
according to Slater's free electron approximation. The second part is
not necessarily spherically symmetric. Birman studied this potential
along three crystallographic directions, and chose that for the 111 direc-
tion to use in the band calculation, multiplied by a constant so that
the sum of parts one and two would be zero midway between nearest
neighbors.
The cellular method was applied in the band calculation of Shakin
and B i r m a ~ Each
~.~~ of ~the states considered were expanded in a four-
term series of products of radial functions and lattice harmonics. Bound-
ary conditions were applied a t discrete points on the bounding surface
between zinc and sulfur polyhedron. Eigenvalues were found at three
symmetry points: l?, L,and X . From the preliminary results reported,
it appears that the valence band maximum and conduction band mini-
mum are both a t k = 0 (states r,) and "1, respectively), and that the
minimum band gap (at k = 0) is about 6 to 8 ev.
51. BARIUM OXIDE
A cellular method calculation of energy bands in barium oxide has
been made by Morita and H ~ r i e The . ~ ~calculation
~ is similar in many
respects to that of Ewing and Seitz for LiF.270 The crystal potential was
taken from self-consistent field calculations of the 1s wave functions for
0- and for the 1s through 4d levels of Cs+. Exchange interactions were
not included in the band calculation, but an approximate correction for
exchange was computed a t the end. The Madelung potential was com-
a75 A. Morita and C. Horie, Sci. Repts. T8hoku Univ., First Ser. S6, 259 (1952).
2 10 JOSEPH CALLAWAY
puted according to the ionic model with an effective charge of 2. Energy

levels in the bands formed from the 2s and 2p levels of oxygen and the 5p
of barium were studied. It is not clear that enough spherical harmonics
were included to satisfy the boundary conditions adequately. The 2p
and 5p bands overlap, but corresponding levels in the 2p band are higher
than in the 5p. The order of levels in these bands are in agreement with
the normal level order in the face-centered cubic lattice. The 2p band
was found to be about six volts wide, and to have its highest energy at
-7.2 ev. The gap between the 2p band and the conduction band was
found to be 10.4 ev after all corrections. Sproull in the A.I.P. Handbook
estimates the experimental gap to be 4.2 e ~ . ~ 7 6
52. MISCELLANEOUS
MATERIALS
Yamazaki, has reported tight binding calculations of energy levels in
metallic b o r i d e ~and
~ ~in~ boron c ~ rb i d e . ~Rather
~B drastic assumptions
concerning the symmetry had to be made in order to simplify the sym-
metry so calculations would be possible in these complicated structures.
Very crude approximations were made to estimate potential integrals
involving direct and nearest neighbors. It was found that the borides,
an example of which is CaBs, should be semiconductors if the metal
atoms have two valence electrons. Solutions of the 25 X 25 determinental
equation were examined a t symmetry points and along symmetry axes
of a simplified Brillouin zone. Numerical estimates for CaB6 gave an
energy gap of 1.5 ev.
I n boron carbide, B&, the crystal structure is built up of icosahedra
containing twelve boron atoms and linear chains of three carbon atoms,
all arranged in a rhombohedra1 giant lattice. Since there are fifteen
atoms per unit cell, the secular determinant is 60 X 60. The symmetry
was simplified by considering the carbon atoms in a chain en bloc and
the boron atoms in an icosahedra en bloc. The secular equation was
solved for two points within the simplified Brillouin zone. Consideration
of the compatibility relations showed that it was possible to obtain an
energy gap between the completely full valence bands and empty con-
duction bands.
VII. Conclusions and Prospects
The survey of existing calculations of energy bands indicates that
tremendous progress has been made in determining the level spectrum
associated with a given potential. The contrast between present-day
applications of the cellular or the OPW method and the prewar work is
2’6 R. L. Sproull in “American Institute of Physics Handbook” (D. E. Gray, ed.),
pp. 5-158. McGraw-Hill, New York, 1957.
*77 M. Yamazaki, J . Phys. SOC.Japan 12, 1 (1957).
2’8 M.Yamazaki, J . Chem. Phys. 27, 746 (1957).
very striking. Agreement between theory and experiment is now becom-

ing a valid test of the initial assumptions, particularly of the adequacy
of a given potential. Much work remains to be done before calculations
for systems other than the simplest metals are reasonably self-consistent.
This problem is particularly important for semiconductors and the
transition metals.
It is desirable, of course, to do more than test the adequacy of an
assumed potential. One wishes to ascertain the ability of the one-electron
approximation to predict the results of experiments. A real answer to
this question cannot be given until more progress has been made in
achieving self-consistency. There are, however, three points which stand
out prominently a t the present time: (1) The language of the theory is
adequate to describe a large number of phenomena in semiconductors
and in metals. (2) There is a large region of qualitative agreement between
theory and experiment. (3) Quantitatively, the results tend to be some-
what disappointing.
The ability of the one-electron approximation to furnish a framework
for the description of experiments is most apparent in semiconductors. A
large range of electrical, optical, and thermal properties can be explained
in terms of a band model whose basic parameters, the effective masses,
are determined by direct experiment. This is a very impressive success;
the reasons for it are understood qualitatively. The theory is also reason-
ably successful in this respect in metals. X-ray experiments demonstrate
the existence of a well-defined Fermi surface; other experiments, such
as the de Haas-van Alphen effect and related experiments reveal many
of its features. There are, however, other phenomena in metals for which
the situation is less clear. The situation is quite confused in the alkali
halides, because crystal imperfections are important and the interaction
between electrons and the lattice vibrations is strong. Phenomena which
are described more readily in terms of an atomic model rather than a
band theory do seem to exist.
Calculations of energy bands usually have a measure of qualitative
agreement with experiment. In germanium, for example, the theory
predicts that the top of the valence band is a doubly degenerate state
(if spin is not counted) and predicts the existence of heavy and light
holes. However, quantitative results are not achieved. The energy gaps
and the effective masses are not given accurately, nor is the minimum of
the conduction band located properly. It will be extremely interesting
to see to what extent more accurate calculations improve the situation.
The situation is similar in metals. In aluminum, for example, Heine
found that pockets of holes should lie in the neighborhood of W , if they
actually exist. This prediction is indicated by the experiments, however,
Heine was not able to demonstrate their existence unambiguously from
212 JOSEPH CALLAWAY
the theory. The situation seems to be most favorable in the alkali metals.
Good results are obtained for the cohesive energy and related quantities
although it must be admitted that agreement is attained only after the
correlation energy term is included. The Knight shift seems to be pre-
dicted reasonably well. There are indications that it will be possible to
account for the effective masses on the Fermi surface. We may emphasize
again that in studying the properties of metals it is never adequate to
treat the interaction between the valence electrons entirely in terms of
the one-electron theory alone.
Those calculations which strive for a greater degree of self-consistency
will have special merit in the future from the theoretical point of view.
Moreover, there seems to be an opportunity for semiempirical studies
analogous to the work of Kane and of Phillips. Progress in our knowledge
of electron interaction is most urgently needed. The role this interaction
plays in ferromagnetism must be determined. Experimentally, more effort
should be made to obtain quantitative information concerning the Fermi
surface in metals. This is particularly true for the alkali metals in which
the theory stands the best chance of explaining experimental observations.
Measurements of the electronic specific heat, the optical properties, the
anomalous skin effect, and cyclotron resonance should be extended. It is
recognized, of course, that serious practical problems arise in carrying
through such experiments; however, the possibility of detailed compari-
son between theory and experiments should be a stimulus to the effort.
A detailed way of determining features of the band distribution well
above the Fermi surface is still lacking. Measurements of x-ray absorp-
tion and electron energy loss may be useful in this respect. There still are
theoretical problems to be overcome before the measurements provide
useful tools in a quantitative sense. The role played by the hole in the
inner atomic shells in determining the x-ray spectra will have to be
ascertained; careful calculations of transition probabilities will have to
be made. The effect of the plasma oscillations in determining the energy
loss of electrons must be studied further. A careful calculation of the
energy loss spectrum for a simple metal on the basis of interband transi-
tions would help considerably in this respect.
The author wishes to thank Dr. J. Goldman and the staff and manage-
ment of the scientific laboratory of the Ford Motor Company for their
hospitality during the summer of 1957, when this review was begun. The
work of the author a t the University of Miami has been supported by
the Office of Naval Research and the Air Force Office of Scientific
Research. Dr. Conyers Herring kindly read the manuscript prior to
publication.

(Solid State Physics) Volume 7 - Electron Energy Bands in Solids by Callaway, Joseph (1958)

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(Solid State Physics) Volume 7 - Electron Energy Bands in Solids by Callaway, Joseph (1958)

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Electron Energy Bands in Solids

V. The Transition Metals.. ............................................ 180

1. Introduction and General Theory

in which uk(r) is periodic in r with the periodicity of the potential. This

pression that energy bands are found only in periodic structures. It is

we construct all the possible N by N determinants out of the one-body

determined. It also appears that many excitations of low-energy can be

3. THE HARTREE-FOCK EQUATIONS

approximation. The interpretation of this equation is discussed in the

where V . and Vex are ordinary and exchange potentials respectively.

It is apparent that the principal physical problem in a calculation band

1) J. C. Raterl Plcys. Rev. 81,385 (1951).

16 F. Seitr, “The Modern Theory of Solids.” McGraw-Hill, New York, 1940.

Dresselhaus.20Elliotta1has discussed the double group (spin included), as

6. BEHAVIORO F A BANDNEAR A DEGENERACY

The equation for k = ko + s is

can be treated as a perturbation.

I. eband bcc fcc

11. p band bcc fcc

IV. f band rz6 rot

of a hexagonal face. The levels Wi and W 3are degenerate in the empty

tions. These expansions must be terminated after a finite, and relatively

II. The Alkali Metals

The preceding paragraph summarizes the theory of the cohesive

Silverman's results are (to order k2)

The equation satisfied by auo/aE is

The Fermi energy is found to be

sphere is maintained. However, a large value of El(') probably implies

The principal difEculty encountered by the quantum defect method

14. RELATIVISTIC EFFECTS

Unfortunately, existing self-consistent fields for free atoms usually do

Silverman and Kohn and Brooks Brown and

Eo -0.6832 -0.6832 -0.6865 -0.6863 -0.6827

lattice constant ra = 3.21 except a noted). The cohesive energy of

EB= Eo - Ea + 2.21E2/ra2+ 5.81E4/ra4. (15.1)

6) M. L. Glwer and J. Callaway,Phys. Rev. 109, 1541 (1958).

68 E. Brown and J. A. Krumhansl, Phys. Rev. 109,30 (1958).

EX is the energy of electron interaction calculated with Wigner’s

The cohesive energy is -E, = EB + EX.

EB = -0.1384 (ry) = -43.2 kcal/mole

The QDM calculation of BrooksBQ leads to a value of -0.1399 ry for EB

makes a significant contribution to the orthogonality coefficients. Also,

potential of the valence electron distribution cannot appreciably affect

posal waa introduced in an attempt to explain the soft x-ray emission

Q J. Bardeen, J . Chem. Phys. 6, 367 (1938).

The cohesive energy is given in Table VI according to the band pa-

it is curious that the net effect of the Coulomb interaction is an increase

TABLEVI. Comsm ENEEGY

EB = -0.0814 (ry) = -25.5 kcal/mole

energy and lattice spacing (24.7 kcal/mole and a lattice constant of

The constants A and B were adjusted so that agreement is obtained with

The cohesive energy of potassium can be computed on the basis of the

77 5. Berman, J. Callaway, and R. D.Woods,Phys. Rev. 101, 1467 (1956).

be to scale the polarization potential on the basis of the values of Van

"IS-' PI- N2--

sufficient to answer most questions regarding the order of levels. Some of

The heavier alkali metals have not been studied as extensively as

TABLE FOR RB AND Cs

Callaway and Callaway and

Eo = -0.462 -0.4442 -0.4258 -0.4156 -0.4274

Rb Rb (Callaway and Morgan)

EB = -0.0651 = 20.4 kcal/mole EB = -0.053 ry = 16.6 kcal/mole