Structure and Bonding in Crystalline Materials: A Textbook for

Materials Science and Engineering Students

Gregory S. Rohrer
Department of Materials Science and Engineering
Carnegie Mellon University
Pittsburgh, Pennsylvania 15213-3890

The Journal of Materials Education, 20 (1998) 135.

correspondence should be addressed to G.S. Rohrer at:

phone

412-268-2696

fax

412-268-7599

e-mail

gr20+@andrew.cmu.edu

www

http://neon.mems.cmu.edu/rohrer.html

G.S. Rohrer

p. 2

ABSTRACT

A textbook has been prepared for an entry level Materials Science and Engineering graduate
course on structure and bonding in crystalline materials. The course is intended to serve as
a foundation for other graduate courses by providing techniques to understand crystal
structures and the cohesive forces that stabilize them. The intrinsically connected topics of
structure and bonding are presented in the same course because without knowledge in both
of these areas, it is not possible to address the fundamental relationship between the
composition, structure, and properties of solid matter that motivates nearly all materials
research.

The purpose of this paper is to describe the rationale used during the

development of the course and the textbook that has been prepared to assist Materials
Science and Engineering students and instructors.

Keywords:
Textbook, Crystal Structures, Bonding in Crystals

G.S. Rohrer

p. 3

INTRODUCTION
The interdisciplinary nature and continual evolution of the field of Materials Science
and Engineering (MSE) make the choice of a core graduate curriculum a difficult issue.
Nevertheless, most departments select a small subset of courses that are required for all
graduate students. Ideally, the material taught in the core part of the curriculum will
provide all students (even those with undergraduate training in other disciplines) with the
tools necessary to address the central issue that motivates nearly all materials research: how
does the composition of solid matter and the way in which it is processed influence its
structure and properties? To explore this fundamental question in a systematic manner, one
needs to understand how the structure of matter is described, how to experimentally probe
structure, and the cohesive forces in solids that determine the structure. The scope of the
course described here is limited to descriptions of ideal atomic structure (the defect structure
and microstructure being course material unto themselves), the theory of diffraction,
bonding in crystals, and the relationship between structure and bonding.
The intellectual match between the topics of crystal structure and bonding is difficult
to dispute. This structure-bonding relationship was realized in the early part of the century
and discussed extensively through the decades by Pauling [1], Hume-Rothery [2], Pearson
[3], Phillips [4], and Villars [5-7].

However, the graduate curricula in most MSE

departments continue to greatly emphasize structure over bonding. In many cases, students
are exposed to advanced models for crystal cohesion only during courses on electrical
properties or solid state physics. Clearly, there is a potential advantage to teaching the topic
of crystal cohesion at the same time as the topic of crystal structures so that the connections
can be emphasized.
There are numerous existing books on crystallography [8-11], structural solid state
chemistry [12,13], metallurgy [14], and solid state physics [15-17] that can be used as
resources when teaching a course on structure and bonding. However, none of these
books is wholly appropriate and this means that one must select sections of each. In my

G.S. Rohrer

p. 4

experience, this complicates the instructor's task of educating and the student's task of
learning. The motivation for preparing this textbook was to provide a self-contained,
coherent resource for both students and instructors. I should mention that another book
targeted for MSE curricula, "Structure and Bonding in Condensed Matter", by C.S.
Nichols [18], appeared three years ago. The textbook described here differs from this
mainly in the balance between the two topics. The book by Nichols, which is no longer in
print, has greater detail in the quantum mechanical models for bonding, while the book
described here has a more extensive description of crystal structures, diffraction, and
phenomenological models for bonding.

THE SUBJECT MATTER AND ITS ORGANIZATION

The most important (and possibly contentious) organizational decision in the

structure of the textbook was whether to present structure or bonding first.

There are

reasonable philosophical and pragmatic arguments for both possible arrangements. For
example, it has been argued that the distribution of electrons in the solid (the bonding)
determines the structure and, therefore, bonding must be presented before structure. While
this view can be supported, it leads to two problems. The first is the implication that the
relationship between bonding and structure is a one way street.

In fact, the atomic

configuration in a crystal and the electronic distribution (spatial and energetic) seek a joint
equilibrium. Consider, for example, what happens when a phase transformation is initiated
by the application of hydrostatic pressure.

In this case, the interatomic distances are

externally altered and the bonds respond to the structure by changing to a new
configuration.

The second problem with presenting the bonding section before the

structure section is that it betrays the scientific process. Models to explain phenomena are
developed based on observations. Models for chemical bonds in solids were developed
only after extensive crystallographic studies. When examining a model, it is essential that

G.S. Rohrer

p. 5

one has a strong working knowledge of the phenomenon being explained. Since crystal
structure data are the observations on which bonding models have been formulated, I have
chosen to present this section in advance of the bonding models. A complete table of
contents for the text is presented in Table 1.
The case for presenting structure before bonding can also be argued from a
pragmatic standpoint. The development of every analytical model for bonding is based on
an understanding of the periodicity of the Bravais lattice and symmetry. Furthermore, the
concepts of the reciprocal lattices, plane wave scattering, and systematic absences are
easiest to introduce when describing diffraction, where the relationships between atomic
structure and the reciprocal lattice (diffraction pattern) are concrete. It is then much easier
to use these tools to describe the nearly free electron theory, the stability of electron
compounds, and the reduced zone scheme for the presentation of band structures.
The decision to present the structure section before the bonding section is hedged
somewhat by the first, introductory chapter. In Chapter 1, simple models for crystal
structures and bonding are introduced. It is assumed that for most students in the course,
this is a review. However, it does provide a foundation in bonding models before the
beginning of the structure section. There are two points of emphasis in this chapter: the
periodic nature of bonding, structure, and properties and the weakness of the simple
models that most students were exposed to as undergraduates. This is intended to motivate
the more detailed sections that follow.
Chapters 2 though 5 comprise the structural section of the course. Chapter 2 is a
review of undergraduate crystallography with all of the terminology and mechanics needed
for any advanced discussion. For example, the chapter includes sections on the real space
lattice, crystallographic notation for locations, directions and planes, the reciprocal lattice,
methods for calculating geometric parameters of the lattice, and methods for representing
crystal structures. I have found that this is not only a useful review for MSE students, but
it also provides an adequate foundation for students from other disciplines.

G.S. Rohrer

p. 6

The third chapter describes the formal methods used to specify the symmetry of a
crystal. The symmetry groups and operators used by crystallographers are a concise set of
instructions for generating the positions of the atoms in a crystal. The goal of the chapter is
not to explain the theory of groups, but to provide students with the information necessary
to interpret crystallographic data written using conventional notation. This chapter contains
sections on symmetry operators, the 32 crystallographic point groups, the 230
crystallographic space groups, and the interpretation of standard crystallographic data.
The goals of the fourth chapter are to acquaint the student with typical prototype
crystal structures and to present a less formal, but more convenient way of describing
structures. Briefly, simple structures are described as eutactic arrays with an ordered
occupation of close-packed and/or interstitial sites. While this method lacks the precision
of the one presented in Chapter 3, it is valuable because it leads to easy visualization and
provides a means for comparison. More complex ternary and quaternary structures are
described in comparison to the simple ones and noncrystalline structures (quasicrystalline,
incommensurate, liquid crystalline, and amorphous structures) are described briefly in the
last section.
The following example illustrates the methods emphasized in the first several
chapters of the book. Chapters 3 and 4 include data for more 50 structure types in the
format illustrated by Tables 2 and 3. In a worked problem, the reader is asked to describe
the packing in the scheelite structure, compare this ternary structure to a more well known
binary prototype structure, and to develop a geometric criterion that can be used to
differentiate the ABO4 compounds that take the scheelite structure from those that take the
rutile structure. Based on the data in Table 3 and the information provided in Chapters 2
and 3, the schematic in Fig. 1 is constructed. From this sketch, we recognize that the metal
atoms occupy the sites of a cubic close packed lattice and that the oxygen occupy the
tetrahedral interstices. Based on this packing description, we note a similarity to the
fluorite structure. However, scheelite differs from fluorite because the ordering of the two

G.S. Rohrer

p. 7

metal atoms on the close packed sites doubles the length of the unit cell along [001]. This
ordering of the two metal atoms also causes the O to occupy a position that is distorted
form the ideal tetrahedral coordination. To develop a geometric criterion to separate those
ABO4 compounds that take the rutile structure from those that take the scheelite structure,
we recall that in rutile all of the metal atoms are 6-coordinate. In scheelite, the A cations are
8-coordinate while the B cations are 4-coordinate. This suggests an A/B size differential.
To test this, the data in Tables 2 and 3 are used to make the plot in Fig. 2, which clearly
illustrates that if rA/rB < 1.3, the rutile structure is preferred over scheelite.
The goal of the fifth chapter is to provide students with enough of a foundation in
the theory of diffraction that they understand how structures are determined and what
typical data mean. Rather than surveying crystallographic techniques or methods (most
MSE departments devote an entire course to this subject), the chapter concentrates on the
theory that accounts for diffraction. An emphasis is placed on understanding how the
lattice and the basis of a structure can be determined from the angular positions and
intensities of diffracted peaks, respectively. Intensity calculations are used to determine
relative site occupations and specific position parameters. This particular section is placed
after the chapters on basic crystallography and symmetry because it is not possible to have
a detailed discussion of diffraction without the mechanical skills for dealing with real space
and reciprocal space lattices or knowledge of the symmetry operations that lead to
systematic absences.
The section on bonding is found in Chapters 6 through 9. Chapter 6 is about
secondary bonding, Chapter 7 is about ionic bonding, Chapter 8 is about metallic bonding,
and Chapter 9 describes the linear combination of atomic orbitals (LCAO) method that can
be used for the whole range of polar covalent bonding. While the subject is divided under
the traditional headings, the book always emphasizes that the first three classifications
(secondary, ionic, metallic) are simply limiting cases of a single phenomenon that should
simply be called chemical bonding.

In each case, the emphasis is placed on making

G.S. Rohrer

p. 8

quantitative calculations of structural parameters and stabilities. The order of presentation

was selected for the simple reason that there is an escalation in the skills needed for each
model. Chapter 6, on secondary bonding, introduces the Lennard-Jones pair potential and
the methods used to account for long range forces.
In Chapter 7 on ionic bonding, the Madelung potential is added to the LennardJones pair potential. The fundamental steps involved in ionic bond formation are also
described in terms of the Born-Haber cycle. Effects not included in the quantitative model,
including the crystal field stabilization energy and ionic polarization, are assessed. The
concept of electronegativity (first introduced in Chapter 1) is revisited and different
quantitative scales are described. Finally, the ability to predict structure based on these
models is discussed.
The eighth chapter is about metallic bonding and begins with the development of the
free electron theory. After pointing out that this provides no cohesion for the crystal,
electrostatic terms are introduced so that the stability of metallic crystals can be explained.
Next, the nearly free electron theory and dispersion in the reduced zone scheme are
described to introduce the concepts of energy bands, zone boundaries, and energy gaps.
The objective of the ninth chapter is to describe the polar covalent bond within the
framework of the LCAO model. In this final chapter on bonding, I note that the LCAO
model can, in its limits, also be used to describe materials that are considered ionic or
metallic in the simple models. This fact emphasizes the idea that chemical bonding is a
single phenomenon that can be described by a single model. After a brief description of
how the LCAO method is applied to small molecules, it is applied to two dimensional
homopolar crystals, polar crystals, and three dimensional crystals. The Freidel model is
used to explain the presence of covalent bonds in transition metal crystals. The factors that
lead to hybridization and tetrahedral geometries are also described. While this chapter will
not make the student an expert in electronic structure methods, it will provide the
foundation needed to understand the electronic structure of a crystal well enough to

G.S. Rohrer

p. 9

interpret the band structure diagrams and density of states plots that are the common result
of modern theoretical studies.
The methods emphasized in Chapter 9 are illustrated by the following example.
The reader is asked to consider a 2 dimensional binary compound (AB) with a square lattice
structure where each site in the lattice is alternately occupied by an A or B atom. Assuming
that each atom has a single s valence orbital, the reader is asked to apply the nearest
neighbor LCAO model and determine the dispersion along the [100] direction, plot the
dispersion assuming that the hypothetical compound is LiCu, LiAl, and LiCl, and, for each
case, determine the width of the s-derived bands and the gap between the occupied and
unoccupied states.

Although the situation is clearly fictitious and the approximations

unwarranted, the results are instructive (see Fig. 3). The quantitative calculations, which
can be done by hand, illustrate that increasing the polarity in a compound narrows the
widths of the bands and increases the gap between occupied and unoccupied states.
The tenth and final chapter returns to the question that is central to materials
research: How do the composition of solid matter and the way in which it is processed
influence its structure and properties? The scope of this question is much greater than that
of this course, but two parts can be addressed. First, when a given set of elements are
combined, will they react to form a compound, will they dissolve in one another, or will
they be immiscible? Second, what will the ideal atomic scale structure of the combination
be? In this chapter, phenomenological approaches to these questions are reviewed because
they have been more effective than the quantitative physical models. In the first section,
Miedema's [19] and Villars' [20] methods for predicting the existence of stable compounds
are reviewed. In the next section, special electron concentration and radius ratio rules are
reviewed.

Laves phases, interstitial compounds, and Hume-Rothery rules [2] are

described. The next section describes the factors that determine structure in polar covalent
crystals. Among the topics described in this section are Pauling's rules [1] and the bond

G.S. Rohrer

p. 10

valence method [21]. In the final section, structure stability maps developed by Mooser
and Pearson [3], Phillips [4], and Villars [5-7] are described.
Throughout the book, an emphasis is always placed on quantitative data, numerical
examples, and problem solving. For example, the extensive data allow students to examine
how chemical periodicity, electronic structure, and size factors influence structure selection.
In the chapter on diffraction, all of the data needed for the calculation of diffraction peak
intensity are included and sample calculations are carried out. The bonding models in
Chapters 6-9 are all presented in such a way that quantitative solutions can be determined
using simple calculations. In this regard, the methods and parameters established by
Harrison [17] are followed. While these models are not at the state-of-the-art, they are
qualitatively accurate and have the advantage of being simple enough that numerical results
for specific compounds and elements are readily obtained and compared by the student.
Whenever appropriate, the text includes worked numerical examples and each chapter
concludes with an extensive set of problems.

THE COURSE'S TIMING AND TRACK RECORD

In the MSE department at Carnegie Mellon University, this course is taught to all
first semester graduate students. A smaller number of senior MSE undergraduates and
graduate students from Chemical Engineering, Electrical and Computer Engineering,
Mechanical Engineering, and Physics also enroll. The class is held on a normal semester
schedule and meets for 28, 110 minute lectures. The chapter structure of the text book is
by no means evenly divided. The approximate schedule that I have used is illustrated in
Table 4. This is covers 26 of 28 lecture periods and leaves two exam and/or review
classes.
I have taught this course annually since 1992 and each class has consisted of 17 to
27 students; the total number of students that have taken this course is 130. At the end of

G.S. Rohrer

p. 11

each semester, students are asked the question, "What was the overall quality of this
course?" The response is an integer rating, from 1 to 5, with 5 being the best. The results
for the first 5 years (the 1997 results are not yet available) are summarized in Table 5. As a
baseline for the rating system, consider the fact that this question is asked of every student
in every class in the college and the mean for all courses taught during the same five years
was 3.98.
In the first year, there was no text for the course. Students were asked to read from
one of about 10 different existing books before each lecture. During this period, the course
was rated as slightly above average. The second year was much the same, but I made a
transcribed version of my lecture notes available to students a few days before each lecture.
During this year, the course was rated well below the college average. Before the third
year, I organized, corrected, and greatly expanded the transcription of the notes and made a
draft version of the book available to the class before the semester. This draft version was
the primary source for the class. At this point, the students' opinions of the class improved
significantly. During subsequent years, the content and the organization of the book were
continuously refined and the ratings of the course have also improved.

CONCLUSION

A textbook has been prepared from which it is possible to teach the topics of crystal
structures and crystal cohesion in an integrated way. Student approval of a course based
on this text has been high. Currently, there are no firm plans for publication. However, I
anticipate that in the near future, this book will be available for use by others; students and
instructors interested in this text prior to publication are encouraged to contact the author.

ACKNOWLEDGMENT

G.S. Rohrer

p. 12

I thank the National Science Foundation for support under a YIA grant DMR-9458005.
REFERENCES
[1] L. Pauling, J. Am. Chem. Soc., 51 1010 (1929).
[2] W. Hume-Rothery, G. Raynor, "The Structure of Metals and Alloys" (Institute of
Metals, London 1962).
[3] E. Mooser and W. B. Pearson, Acta Cryst, 12 1015 (1959).
[4] J.C. Phillips, Rev. Mod. Phys., 42 317 (1970).
[5] P. Villars, J. Less-Common Metals, 92 215 (1983).
[6] P. Villars, J. Less-Common Metals, 99 33 (1984).
[7] P. Villars, J. Less-Common Metals, 102 199 (1984).
[8] D.E. Sands, "Introduction to Crystallography" (W. A. Benjamin, New York 1969).
[9] M.J. Buerger, "Contemporary Crystallography" (McGraw Hill, New York 1970).
[10]

H. Megaw, "Crystal Structures: A Working Approach" (W. B. Saunders,

Philadelphia 1973).
[11]

B.D. Cullity, "Elements of X-ray Diffraction, 2nd edition" (Addison-Wesley,

Reading, MA 1978).
[12] A.F. Wells, "Structural Inorganic Chemistry, 5th edition" (Clarendon Press, Oxford,
1984).
[13]

A.R. West, "Solid State Chemistry and its Applications" (J. Wiley & Sons,

Chichester 1984).
[14] C.S Barrett and T.B. Massalski, "The Structure of Metals" (McGraw Hill, New York
1966).
[15] C. Kittel, "Introduction to Solid State Physics 5th edition" (J. Wiley & Sons, New
York 1976).
[16] N.W. Ashcroft, N.D. Mermin, "Solid State Physics" (Holt Rinehart and Winston,
New York 1976).

G.S. Rohrer

p. 13

[17] W.A. Harrison,"Electronic Structure and the Properties of Solids: The Physics of the
Chemical Bond" (Dover Publications, Inc., New York 1989).
[18] C.S. Nichols, "Structure and Bonding in Condensed Matter" (Cambridge University
Press, Cambridge, 1995).
[19] D.G. Pettifor, Solid State Physics 40 43 (1987).
[20] P. Villars, J. Less-Common Metals 109 93 (1985).
[21] M. O'Keeffe and N.E. Brese, J. Am. Chem. Soc., 113 3226 (1991).

G.S. Rohrer

p. 14

Figure Captions

Figure 1. A sketch of the atomic positions in the scheelite structure. The projection is
shown along the [100] direction.

Figure 2. The radius ratios for the rutile and scheelite structured ABO4 compounds listed
in Tables 2 and 3, respectively. For a consistent comparison, the octahedral radii are used.

Figure 3. Dispersion relations for three hypothetical Li compounds. (a) The two different
atoms alternately occupy the vertices of a square lattice. (b) The dispersion of electron
energy levels along [100] for three combinations of atoms. The dispersion relation, or
energy (E) as a function of wave vector, (k), is shown below. EA is the term state for the
valence s electron of the A atom and EB is the term state for the valence s electron of B
atoms. Vss is the covalent energy for the overlap of the s states, and r1 and r3 are the
vectors defined in (a).

G.S. Rohrer

p. 15

0.11

0.89

0
0.25 0.75

0.89
0.5

0.11
0

0.25 0.75
0.25 0.75

0.5
0.89

0.5
0.11

0.5
0.75 0.25

0
0.75

0.5

= Ca

0.61

0.25

0.39

0.11

0.89
0.5

=W
=O

0.5

0.61

Figure 1. G.S. Rohrer

0.39
c

G.S. Rohrer

p. 16

scheelite
rutile

Smaller Cation Radius,

0.7
0.65
0.6

ra = r b

0.55
0.5
0.45
0.4
0.35
0.3
0.3

0.6

0.9

1.2

Larger Cation Radius,

Figure 2. G.S. Rohrer

1.5

1.8

G.S. Rohrer

p. 17

r3
r1

vacuum level (unbound)

Energy, eV

-5

-10

-15
-20

-25

LiCu

-30
0

[kx,0,0]

E(k) = 1/2(EA+EB)

Figure 3. G.S. Rohrer

LiAl
/a 0 [kx,0,0]

LiCl
/a 0

[kx,0,0]

/a

1/4(EA-EB)2 + {2Vss[coskr1+coskr 3]}

G.S. Rohrer

p. 18

Table 1. Table of Contents for Structure an Bonding in Crystalline Materials

1. Chapter 1, Introduction
A. Introduction
B. The Importance of the Periodic Table: Mendeleev Predicts Ge in 1871
C. Periodic Trends in Atomic Properties
D. Bonding Generalizations Based on Periodic Trends in the Electronegativity
(i) Classification of the elements
(ii) Simple bonding models and typical properties
(iii) Ketelaar's triangle
(iv) Examples of trends in bonding
E. Generalizations About Crystal Structures Based on Periodicity
(i) Close-packing in metallic solids
(ii) Radius ratios in ionic structures
(iii) Orbital hybridization in covalent structures
(iv) Examples of periodic trends in structures
F. The Limitations of Simple Models
(i) Polymorphism
(ii) Systems with mixed properties and mixed bonding
G. Problems
H. References and Sources for Further Study
2. Chapter 2, Basic Structural Concepts
B. The Bravais Lattice
(i) Definition
(ii) Geometry of the 14 three dimensional Bravais lattices
C. The Unit Cell
(i) The primitive cell
(ii) The non-primitive conventional cell
(iii) The Wigner-Seitz cell
D. The Crystal Structure. A Bravais Lattice Plus a Basis
E. Specifying Locations, Planes and Directions in a Crystal
(i) Locations
(ii) Directions
(iii) Indices for planes
F. The Reciprocal Lattice
(i) Mathematical formalism
(ii) The relationship between the direct lattice and the reciprocal lattice
(iii) The first Brillouin zone
G. Quantitative Calculations Involving the Geometry of the Lattice
(i) The distances and angles in the direct lattice
(ii) Interplanar spacings, angles between planes, and cell volume
H. Beyond the Ball and Stick Representation of Crystals
(i) Polyhedral models
(ii) Block representations
(iii) The stereographic projection
I. Problems
J. References and Sources for Further Study
3. Chapter 3, Symmetry in Crystals
A. Introduction
B. The Symmetry Operators
C. The First Five Symmetry Operators
(i) Definitions
(ii) The distinction between proper and improper operations

1
2
2
3
6
6
7
10
11
14
14
17
21
24
25
25
27
30
31
33
34
34
36
47
47
47
50
50
53
53
53
54
57
57
60
62
64
64
67
71
71
74
78
81
84
85
86
86
87
87
91

G.S. Rohrer

p. 19

Table 1, continued. Table of Contents for Structure an Bonding in Crystalline Materials

D. Combining Operators to Form the 32 Distinct Crystallographic Point Groups
(i) Compatibility of rotations and translations
(ii) Group notation
(iii) Combinations of proper rotations
(iv) Groups formed by improper rotations
E. The 32 Point Groups Classified by Bravais Lattice
(i) Point group nomenclature
(ii) The importance of an inversion center
(iv) Dealing with cubic point groups
(v) General and special positions
(vi) Notes on determining the crystallographic point group of an object
F. The 230 Space Groups
(i) The screw and glide operators
(ii) The origin of the space groups and their symbols
(iii) The space group symbols
(iv) Space group representations
(v) Trigonal and hexagonal groups
(vi) Information in the International Tables
G. The Interpretation of Conventional Crystal Structure Data
H. Problems
I. References and Sources for Further Study
Chapter 4. Crystal Structures
A. Introduction
B. Close-Packed Arrangements
(i) Types of close-packing
(ii) The ccp and hcp arrangements
C. The Interstitial Sites
D. Classifying and Naming Crystal Structures.
E. Close-Packed Metallic Structures
(i) The B2 or CsCl structure
(ii) The L10 or CuAu structure
(iii) The L12 structure
(iv) The DO3 and L21 structures
(v) The DO19 and DO24 structures: hcp superlattice structures.
(vi) Filling the interstices of the bcc lattice: the A15 structure
(vii) The C14, C15, C16 structures
F. Close-Packing in Ionic Compounds
(i) The rock salt and NiAs structures
(ii) The spinel and olivine structures
(iii) The rutile and CdI2 structures
(iv) Other AB2 structures, the CdCl2 and fluorite structures
(v) The perovskite structure
(vi) Superlattice structures
(vii) Extensions of the close-packing description to more complex structures
G. Structures Derived From ReO3
(i) Bronzes
(ii) Structures derived by crystallographic shear
H. Tetrahedral Structures
(i) The sphalerite and wurtzite structures
(ii) Complex structures based on sphalerite and wurtzite

91
91
93
93
95
97
97
99
103
105
108
109
112
113
114
115
124
128
129
145
150
153
154
154
154
157
160
163
165
165
166
167
168
170
172
173
176
176
179
183
185
187
192
193
193
194
195
196
196
198

G.S. Rohrer

p. 20

Table 1, continued. Table of Contents for Structure an Bonding in Crystalline Materials

I. More Complex Packing Sequences
(i) Notation for stacking sequences
(ii) The SiC polytypes
J. Van der Waals Solids
K. Noncrystalline Solid Structures
(i) Incommensurate structures
(ii) Quasicrystalline structures
(iii) Liquid crystalline structures
(iv) Amorphous materials
L. Problems
M. References and Sources for Further Study
5. Chapter 5, Diffraction
A. Introduction
B. Bragg's Formulation of the Diffraction Condition
C. The Scattering of X-rays From a Periodic Electron Density
(i) The periodic electron density
(ii) Elastic scattering
(iii) Scattering from many centers
(iv) Equivalence of the Bragg condition and the elastic scattering condition
(v) The Ewald construction
(vi) Concluding remarks
D. The Relationship Between Diffracted Peak Intensities and Atomic Positions
(i) The structure factor
(ii) Systematic absences due to lattice centering
(iii) Systematic absences due to glide operators
(iv) Systematic absences due to the presence of screw axes
(v) Systematic absences and the reciprocal lattice
E. Factors Affecting the Intensity of Diffracted Peaks
(i) Measuring diffracted beam intensities
(ii) Example of a structure factor calculation
(iii) The atomic scattering factor
(iv) The temperature factor
(v) The Lorentz - polarization factor
(vi) Multiplicity
(vii) Computing the intensities
(viii) Preferred orientation
(ix) The absorption correction
(x) The extinction correction
F. Some Diffraction Techniques and Their Uses
(i) Laue back-reflection
(ii) Powder diffraction
(iii) Single crystal methods
(iv) Electron diffraction
(v) Neutron diffraction
G. Supplementary Information
(i) Basics of the Fourier series
(ii) Coefficients for scattering factors
H. Problems
I. Review Problems
J. References and Sources for Further Study

202
202
202
204
204
204
206
208
209
211
217
219
220
220
222
222
225
230
233
234
236
237
237
242
244
244
247
252
252
254
255
256
258
259
260
262
263
263
264
264
265
268
270
270
272
272
275
276
283
286

G.S. Rohrer

p. 21

Table 1, continued. Table of Contents for Structure an Bonding in Crystalline Materials

6. Chapter 6, Van der Waals Bonding
A. Introduction
(i) Substances held together by van der Waals bonds
(ii) The effect of molecular weight
(iii) The effect of molecular shape
B. A Physical Model for the van der Waals Bond
(i) The origin of molecular attraction and repulsion
(ii) The Lennard-Jones potential energy model
(iii) Calculating the lattice constant, the cohesive energy, and the bulk modulus
(iv) Accounting for longer range interactions
(v) Connecting the generalizations with the physical models
C. Interactions of molecules with permanent dipole moments
D. Problems
E. References and Sources for Further Study
7. Chapter 7, Ionic Bonding
A. Introduction
(i) Solids that are held together by ionic bonds
(ii) The effect of charge and separation on bond strength
(iii) The effect of size on the structure
B. A Physical Model for the Ionic Bond
(i) The formation of an ionic bond
(ii) The ionization energy and electron affinity
(iii) Estimating lattice energies and stability using the Born-Haber cycle
(iv) The Coulombic bonding force and the ionic pair potential
(v) Ionic bonding in the crystal
(vi) The Madelung constant
(vii) Evaluation of the Madelung constant
(viii) Calculating the equilibrium separation, lattice energy, and compressibility
C. Refinements to the Model
(i) The van der Waals attraction
(ii) The zero-point energy
(iii) The crystal-field stabilization energy
(iv) Polarization
D. Predicting the Structures of Ionic Compounds
(i) The minimum energy structure
(ii) Ionic radius and coordination
(iii) The influence of polarization on structure
E. Electronegativity Scales
F. The Correlation of Physical Models with the Generally Observed Trends
G. Problems
H. References and Sources for Further Study
I. Pauling Electronegativities .
J. Table of Ionic Radii
8. Chapter 8, Metallic Bonding
A. Introduction
(i) Materials that are held together by metallic bonds
(ii) Variations in the bond strength
(iii) Qualitative free electron theory

287
288
288
289
291
292
292
294
296
300
303
306
309
311
312
313
313
313
314
316
316
317
320
322
326
328
330
333
336
336
337
337
341
343
343
345
347
349
353
355
358
360
361
364
365
366
366
367

G.S. Rohrer

p. 22

Table 1, continued. Table of Contents for Structure an Bonding in Crystalline Materials

B. A Physical Model for the Metallic Bond Free Electron Theory
(i) Wave functions, operators, and expectation values
(ii) Formulation of the free electron theory
(iii) The energy density of states
(iv) The free electron energy
C. Failures of the Free Electron Theory
D. Electrons in a Periodic Lattice
(i) The relationship between reciprocal space and wave vector space
(ii) Plotting dispersion in the reduced zone scheme
(iii) The nearly free electron theory: the origin and magnitude of the energy gap
(iv) Metals and insulators
E. Correlation of the Physical Models with General Trends
F. Problems
G. Further Reading
9. Chapter 9, LCAO Model for the Polar Covalent Bond
A. Introduction
(i) Which solids have covalent bonds
(ii) The crystal structures of covalent solids
(iii) The effect of polarity and separation on the bond strength and band gap
B. A Physical Model For the Covalent Bond in a Molecule
(i) Atomic orbitals
(ii) The homopolar bond in a diatomic molecule
(iii) The polar covalent bond
(iv) Bond polarity
(v) The general case
C. Physical Model for the Covalent Bond in a Crystal
(i) Introduction
(ii) A homopolar crystal with a square lattice
(iii) The effect of polarity
(iv) The ccp structure
(v) The sphalerite structure
D. Transition Metals
E. Orbital Hybridization
F. The Cohesive Energy of a Covalently Bonded Solid
G. Overview of Results From the LCAO Theory
H. Structural Implications of the LCAO Model
I. Problems
J. Further Reading
10. Chapter 10, Models for Predicting Phase Stability and Structure
A. Introduction
B. Compound formation
(i) Miedema's Rules for Alloy Formation
(ii) Villars' method for predicting compound formation
C. Electron Concentration and Radius Ratio rules for Intermetallic Phases
(i) Hume-Rothery rules and electron compounds
(ii) Laves Phases
(iii) Interstitial Compounds

368
368
371
379
381
394
394
394
396
398
402
405
406
408
409
410
410
411
412
413
414
417
422
425
426
428
428
428
435
442
455
458
462
465
468
470
472
476
477
478
479
479
486
491
491
496
499

G.S. Rohrer

p. 23

Table 1, continued. Table of Contents for Structure an Bonding in Crystalline Materials

D. Factors that Determine Structure in Polar-Covalent Crystals
(i) Pauling's rules
(ii) The bond valence method
(iii) The maximum volume principle
(iv) Cation eutaxy
(v) Sanderson's description of the polar covalent bond
E. Structure Stability Diagrams
(i) Mooser-Pearson Plots
(ii) Phillips ionicity
(iii) Villars' structure stability diagrams
F. Problems
G. References and Sources for Further Study

501
501
505
511
513
516
526
526
531
534
539
540

G.S. Rohrer

p. 24

Table 2. The structure of rutile (C4), titanium dioxide

Formula Unit
Space group:
Cell dimensions:
Cell contents:
Atomic positions:

Examples
compound
TiO2
CrO2
GeO2
IrO2
-MnO2
MoO2
NbO2
OsO2
PbO2
RuO2
SnO2
TaO2
WO2
AlSbO4
CrNbO4

a()
4.5937
4.41
4.395
4.49
4.396
4.86
4.77
4.51
4.946
4.51
4.7373
4.709
4.86
4.510
4.635

TiO2, titanium dioxide

P42/mnm (no. 136)
a = 4.594, c = 2.958
2 formula units
Ti in (2a)
mmm 0 0 0;
O in (4f)
m2m x x 0;
1
( + x,
2
x ~ 0.3
c()
2.9581
2.91
2.859
3.14
2.871
2.79
2.96
3.19
3.379
3.11
3.1864
3.065
2.77
2.961
3.005

x
0.305
0.307
0.302

0.307
0.305

compound
CrSbO4
CrTaO4
FeNbO4
FeSbO4
FeTaO4
GaSbO4
RhSbO4
RhVO4
CoF2
FeF2
MgF2
MnF2
NiF2
PdF2
ZnF2

1 1 1
2 2 2
xx0
1
1
1
1
1
x , ) ,( x , + x , )
2
2
2
2
2

a()
4.57
4.626
4.68
6.623
4.672
4.59
4.601
6.607
4.6951
4.6966
4.623
4.8734
4.6506
4.931
4.7034

c()
3.042
3.009
3.05
3.011
3.042
3.03
3.100
2.923
3.1796
3.3091
3.052
3.3099
3.0836
3.367
3.1335

0.306
0.300
0.303
0.305
0.302
0.303

G.S. Rohrer

p. 25

Table 3. The structure of scheelite, CaWO4

Formula unit
Space group:
Cell dimensions:
Cell contents:
Atomic positions:
Ca
W
O
Examples
compound
AgReO4
AgTcO4
BaMoO4
BaWO4
BiAsO4
CaMoO4
CdMoO4
CeGeO4
HfGeO4
KReO4
KRuO4
KTcO4

CaWO4
I41/a (no. 88)
a = 5.24 , c =11.38
4 formula units
(4b)
(4a)
(16f)

a()
5.378
5.319
5.56
5.64
5.08
5.23
5.14
5.045
4.849
5.675
5.609
5.654

0,0,1/2; 1/2,0,1/4; + I
0,0,0; 0,1/2,1/4; + I
x, y,z; x, y,z; x, y + 1 / 2,1 / 4 z;x,1 / 2 y,1 / 4 z;
y, x, z; y, x, z; y, x + 1 / 2,z + 1 / 4;y,1 / 2 x,z + 1 / 4; + I
x=0.25, y=0.15, z=0.075
c()
11.805
11.875
12.76
12.70
11.70
11.44
11.17
11.167
10.50
12.70
12.991
13.03

compound
NaReO4
NaTcO4
PbMoO4
PbWO4
RbReO4
SrMoO4
SrWO4
ThGeO4
TlReO4
UGeO4
YNbO4
ZrGeO4

a()
5.362
5.339
5.47
5.44
5.803
5.36
5.40
5.14
5.761
5.084
5.16
4.871

c()
11.718
11.869
12.18
12.01
13.167
11.94
11.90
11.54
13.33
11.226
10.91
10.570

G.S. Rohrer

p. 26

Table 4 Approximate Schedule for Structure and Bonding in Crystalline Materials

Chapter Number and Title

Number of Lectures

1. Introduction

1.5

2. Basic Structural Concepts

1.5

3. Symmetry in Crystals

4. Crystal Structures

5. Diffraction

6. Secondary Bonding

7. Ionic Bonding

2.5

8. Metallic bonding

2.5

9. LCAO Model for the Polar Covalent Bond

10. Models for Predicting Phase Stability and Structure

G.S. Rohrer

p. 27

Table 5. Student Evaluations of the Course

Year

Mean Course Rating

Number of Students

1992

4.07

17

1993

3.65

27

1994

4.45

22

1995

4.52

23

1996

4.65

20

1997

NA

21