WHY STUDY Atomic Structure and

Interatomic Bonding?
 An important reason to have an understanding of
interatomic bonding in solids is that in some instances,
the type of bond allows us to explain a material’s
properties. For example, consider carbon, which may
exist as both graphite and diamond. Whereas graphite is
relatively soft and has a “greasy” feel to it, diamond is
one of the hardest known materials in nature. In addition,
the electrical properties of diamond and graphite are
dissimilar: diamond is a poor conductor of electricity, but
graphite is a reasonably good conductor. These disparities
in properties are directly attributable to a type of
interatomic bonding found in graphite that does not exist
in diamond.
2.1 INTRODUCTION
 Some of the important properties of solid materials depend on geometric atomic
arrangements and also the interactions that exist among constituent atoms or
molecules. This chapter, by way of preparation for subsequent discussions,
considers several fundamental and important concepts—namely, atomic
structure, electron configurations in atoms and the periodic table, and the
various types of primary and secondary interatomic bonds that hold together the
atoms that compose a solid. These topics are reviewed briefly, under the
assumption that some of the material is familiar to the reader.
Atomic Structure:
Fundamental concepts
 Each atom consists of a very small nucleus composed of protons and neutrons
and is encircled by moving electrons.1 Both electrons and protons are
electrically charged, the charge magnitude being 1.602 ×1019C, which is
negative in sign for electrons and positive for protons; neutrons are electrically
neutral. Masses for these subatomic particles are extremely small; protons and
neutrons have approximately the same mass, 1.67 ×1027 kg, which is
significantly larger than that of an electron, 9.11 × 1031 kg.
2.1 INTRODUCTION
 Atomic number (Z)
Each chemical element is characterized by the number of protons in the nucleus, or
the atomic number (Z). For an electrically neutral or complete atom, the
atomic number also equals the number of electrons. This atomic number ranges
in integral units from 1 for hydrogen to 92 for uranium, the highest of the
naturally occurring elements.
Atomic Mass
 The atomic mass (A) of a specific atom may be expressed as the sum of the
masses of protons and neutrons within the nucleus. Although the number of
protons is the same for all atoms of a given element, the number of neutrons (N)
may be variable. Thus atoms of some elements have two or more different
atomic masses, which are called isotopes. The atomic weight of an element
corresponds to the weighted average of the atomic masses of the atom’s
naturally occurring isotopes. The atomic mass unit (amu) may be used to
compute atomic weight. A scale has been established whereby 1 amu is defined
as 1/12 of the atomic mass of the most common isotope of carbon, carbon 12
(12C) (A=12.00000). Within this scheme, the masses of protons and neutrons are
slightly greater than unity, and
A=Z+N
2.1 INTRODUCTION
 The atomic weight of an element or the molecular weight of a compound may
be specified on the basis of amu per atom (molecule) or mass per mole of
material. In one mole of a substance, there are 6.022 1023 (Avogadro’s
number) atoms or molecules. These two atomic weight schemes are related
through the following equation:
1 amu/atom (or molecule) = 1 g/mol
 For example, the atomic weight of iron is 55.85 amu/atom, or 55.85 g/mol.
Sometimes use of amu per atom or molecule is convenient; on other occasions,
grams (or kilograms) per mole is preferred.
2.3 ELECTRONS IN ATOMS
Atomic Models
 During the latter part of the nineteenth century, it was realized that many
phenomena involving electrons in solids could not be explained in terms of
classical mechanics. What followed was the establishment of a set of principles
and laws that govern systems of atomic and subatomic entities that came to be
known as quantum mechanics.
 One early outgrowth of quantum mechanics was the simplified Bohr atomic
model, in which electrons are assumed to revolve around the atomic nucleus in
discrete orbitals, and the position of any particular electron is more or less well
defined in terms of its orbital. This model of the atom is represented in Figure
2.1.
2.3 ELECTRONS IN ATOMS
 Another important quantum-mechanical principle stipulates that the energies of
electrons are quantized. that is, electrons are permitted to have only specific values of
energy. An electron may change energy, but in doing so, it must make a quantum jump
either to an allowed higher energy (with absorption of energy) or to a lower energy
(with emission of energy). Often, it is convenient to think of these allowed electron
energies as being associated with energy levels or states. These states do not vary
continuously with energy— that is, adjacent states are separated by finite energies. For
example, allowed states for the Bohr hydrogen atom are represented in Figure 2.2a.
These energies are taken to be negative, whereas the zero reference is the unbound or
free electron. Of course, the single electron associated with the hydrogen atom fills
only one of these states.
 This Bohr model was eventually found to have some significant limitations because of
its inability to explain several phenomena involving electrons. A resolution was
reached with a wave-mechanical model, in which the electron is considered to
exhibit both wavelike and particle-like characteristics. With this model, an electron is
no longer treated as a particle moving in a discrete orbital; rather, position is considered
to be the probability of an electron’s being at various locations around the nucleus. In
other words, position is described by a probability distribution or electron cloud. Figure
2.3 compares Bohr and wave-mechanical models for the hydrogen atom. Both models
are used throughout the
 course of this text; the choice depends on which model allows the simplest explanation.
2.3 Quantum Numbers
 In wave mechanics, every electron in an atom is characterized by four
parameters called quantum numbers. The size, shape, and spatial
orientation of an electron’s probability density (or orbital) are specified by
three of these quantum numbers.
2.3 Quantum Numbers
 Furthermore, electron orbital shapes depend on l. For example s orbitals are
spherical and centered on the nucleus (Figure 2.4). There are three orbitals for a
p subshell (as explained next); each has a nodal surface in the shape of a
dumbbell (Figure 2.5). Axes for these three orbitals are mutually perpendicular
to one another like those of an x-y-z coordinate system; thus, it is convenient to
label these orbitals px, py, and pz (see Figure 2.5). Orbital configurations for d
subshells are more complex and are not discussed here.
2.3 Quantum Numbers
 Furthermore, electron orbital shapes depend on l. For example s orbitals are
spherical and centered on the nucleus (Figure 2.4). There are three orbitals for a
p subshell (as explained next); each has a nodal surface in the shape of a
dumbbell (Figure 2.5). Axes for these three orbitals are mutually perpendicular
to one another like those of an x-y-z coordinate system; thus, it is convenient to
label these orbitals px, py, and pz (see Figure 2.5). Orbital configurations for d
subshells are more complex and are not discussed here.
2.3 Quantum Numbers
 Associated with each electron is a spin moment, which must be oriented either
up or down. Related to this spin moment is the fourth quantum number, ms, for
which two values are possible: +1/2 (for spin up) and -1/2 (for spin down).
A complete energy level diagram for the various shells and subshells using the
wave-mechanical model is shown in Figure 2.6.
2.3 Quantum Numbers
 Pauli exclusion principle, another quantum-mechanical concept, which
stipulates that each electron state can hold no more than two electrons that must
have opposite spins. Thus, s, p, d, and f subshells may each accomodate,
respectively, a total of 2, 6, 10, and 14 electrons.
 Of course, not all possible states in an atom are filled with electrons. For most
atoms, the electrons fill up the lowest possible energy states in the electron
shells and subshells, two electrons (having opposite spins) per state. The energy
structure for a sodium atom is represented schematically in Figure 2.7. When all
the electrons occupy the lowest possible energies in accord with the foregoing
restrictions, an atom is said to be in its ground state.
2.3 Quantum Numbers
 The electron configuration or structure of an atom represents the manner in
which these states are occupied. In the conventional notation, the number of
electrons in each subshell is indicated by a superscript after the shell– subshell
designation. For example, the electron configurations for hydrogen, helium, and
sodium are, respectively, 1s1, 1s2, and 1s22s22p63s1.
 At this point, comments regarding these electron configurations are necessary.
First, the valence electrons are those that occupy the outermost shell. These
electrons are extremely important; as will be seen, they participate in the
bonding between atoms to form atomic and molecular aggregates. Furthermore,
many of the physical and chemical properties of solids are based on these
valence electrons.
 In addition, some atoms have what are termed stable electron configurations—
that is, the states within the outermost or valence electron shell are completely
filled. Normally, this corresponds to the occupation of just the s and p states for
the outermost shell by a total of eight electrons, as in neon, argon, and krypton;
one exception is helium, which contains only two 1s electrons. These elements
(Ne, Ar, Kr, and He) are the inert, or noble, gases, which are virtually unreactive
chemically.
2.4 THE PERIODIC TABLE
2.3 Quantum Numbers
 The alkali and the alkaline earth metals (Li, Na, K, Be, Mg, Ca, etc.) are labeled
as Groups IA and IIA, having, respectively, one and two electrons in excess of
stable structures. The elements in the three long periods, Groups IIIB through
IIB, are termed the transition metals, which have partially filled d electron
states and in some cases one or two electrons in the next higher energy shell.
Groups IIIA, IVA, and VA (B, Si, Ge, As, etc.) display characteristics that are
intermediate between the metals and nonmetals by virtue of their valence
electron structures.
 Electropositive
 Electronegative
2.5 BONDING FORCES AND ENERGIES
 Atomic Bonding in Solids
 An understanding of many of the physical properties of materials is enhanced by a
knowledge of the interatomic forces that bind the atoms together. Perhaps the principles
of atomic bonding are best illustrated by considering how two isolated atoms interact as
they are brought close together from an infinite separation. At large distances,
interactions are negligible because the atoms are too far apart to have an influence on
each other; however, at small separation distances, each atom exerts forces on the others.
These forces are of two types, attractive (FA) and repulsive (FR), and the magnitude of
each depends on the separation or interatomic distance (r); Figure 2.10a is a schematic
plot of FA and FR versus r. The origin of an attractive force FA depends on the particular
type of bonding that exists between the two atoms, as discussed shortly. Repulsive forces
arise from interactions between the negatively charged electron clouds for the two atoms
and are important only at small values of r as the outer electron shells of the two atoms
begin to overlap (Figure 2.10a).
2.3 Quantum Numbers
 Sometimes it is more convenient to work with the potential energies between
two atoms instead of forces. Mathematically, energy (E) and force (F) are
related as

And, for atomic systems,

The minimum in the net energy curve corresponds to the equilibrium spacing, r0.
Furthermore, the bonding energy for these two atoms, E0, corresponds to the energy at
this minimum point (also shown in Figure 2.10b); it represents the energy required to
separate these two atoms to an infinite separation.
2.5 BONDING FORCES AND ENERGIES
 Atomic Bonding in Solids
 An understanding of many of the physical properties of materials is enhanced by a
knowledge of the interatomic forces that bind the atoms together. Perhaps the principles
of atomic bonding are best illustrated by considering how two isolated atoms interact as
they are brought close together from an infinite separation. At large distances,
interactions are negligible because the atoms are too far apart to have an influence on
each other; however, at small separation distances, each atom exerts forces on the others.
These forces are of two types, attractive (FA) and repulsive (FR), and the magnitude of
each depends on the separation or interatomic distance (r); Figure 2.10a is a schematic
plot of FA and FR versus r. The origin of an attractive force FA depends on the particular
type of bonding that exists between the two atoms, as discussed shortly. Repulsive forces
arise from interactions between the negatively charged electron clouds for the two atoms
and are important only at small values of r as the outer electron shells of the two atoms
begin to overlap (Figure 2.10a).
2.5 BONDING FORCES AND ENERGIES
Ionic Bonding
 Ionic bonding is perhaps the easiest to describe and visualize. It is always
found in compounds composed of both metallic and nonmetallic elements,
elements situated at the horizontal extremities of the periodic table. Atoms of a
metallic element easily give up their valence electrons to the nonmetallic atoms.
In the process, all the atoms acquire stable or inert gas configurations (i.e.,
completely filled orbital shells) and, in addition, an electrical charge—that is,
they become ions. Sodium chloride (NaCl) is the classic ionic material. A
sodium atom can assume the electron structure of neon (and a net single
positive charge with a reduction in size) by a transfer of its one valence 3s
electron to a chlorine atom (Figure 2.11a). After such a transfer, the chlorine
ion acquires a net negative charge, an electron configuration identical to that of
argon; it is also larger than the chlorine atom. Ionic bonding is illustrated
schematically in Figure 2.11b.
2.5 BONDING FORCES AND ENERGIES
Ionic Bonding
 The attractive bonding forces are coulombic—that is, positive and negative
ions, by virtue of their net electrical charge, attract one another. For two isolated
ions, the attractive energy EA is a function of the interatomic distance according
to

An analogous equation for the repulsive energy is

Bonding energies, which generally range between 600 and 1500 kJ/mol, are relatively
large, as reflected in high melting temperatures.
2.5 BONDING FORCES AND ENERGIES
Ionic Bonding
 The attractive bonding forces are coulombic—that is, positive and negative
ions, by virtue of their net electrical charge, attract one another. For two isolated
ions, the attractive energy EA is a function of the interatomic distance according
to

An analogous equation for the repulsive energy is

Bonding energies, which generally range between 600 and 1500 kJ/mol, are relatively
large, as reflected in high melting temperatures.
2.5 BONDING FORCES AND ENERGIES
Ionic Bonding
 Interatomic bonding is typified by ceramic materials, which are
characteristically hard and brittle and, furthermore, electrically and thermally
insulative. As discussed in subsequent chapters, these properties are a direct
consequence of electron configurations and/or the nature of the ionic bond.
Covalent Bonding
 A second bonding type, covalent bonding, is found in materials whose atoms
have small differences in electronegativity—that is, that lie near one another in
the periodic table. For these materials, stable electron configurations are
assumed by the sharing of electrons between adjacent atoms. Two covalently
bonded atoms will each contribute at least one electron to the bond, and the
shared electrons may be considered to belong to both atoms. Covalent bonding
is schematically illustrated in Figure 2.12 for a molecule of hydrogen (H2). The
hydrogen atom has a single 1s electron. Each of the atoms can acquire a helium
electron configuration (two 1s valence electrons) when they share their single
electron (right side of Figure 2.12).
2.5 BONDING FORCES AND ENERGIES
Covalent Bonding

Many nonmetallic elemental molecules (e.g., Cl2, F2), as well as molecules containing
dissimilar atoms, such as CH4, H2O, HNO3, and HF, are covalently bonded. Furthermore, this
type of bonding is found in elemental solids such as diamond (carbon), silicon, and germanium
and other solid compounds composed of elements that are located on the right side of the
periodic table, such as gallium arsenide (GaAs), indium antimonide (InSb), and silicon carbide
(SiC).
Covalent bonds may be very strong, as in diamond, which is very hard and has a very high
melting temperature, 3550 C (6400 F), or they may be very weak, as with bismuth, which
melts at about 270C (518F).
Inasmuch as electrons participating in covalent bonds are tightly bound to the bonding
atoms, most covalently bonded materials are electrical insulators, or, in some cases,
semiconductors.
Mechanical behaviors of these materials vary widely: some are relatively strong, others
are weak; some fail in a brittle manner, whereas others experience significant amounts
of deformation before failure. It is difficult to predict the mechanical properties of covalently
bonded materials on the basis of their bonding characteristics.
Bond Hybridization in Carbon
Often associated with the covalent bonding of carbon (as well other nonmetallic
substances) is the phenomenon of hybridization—the mixing (or combining) of
two or more atomic orbitals with the result that more orbital overlap during
bonding results.
 Sp3 Hybridization
Sp2 Hybridization
Sp2 Hybridization
Metallic Bonding
Metallic bonding, the final primary bonding type, is found in metals and their alloys. A
relatively simple model has been proposed that very nearly approximates the bonding scheme.
With this model, these valence electrons are not bound to any particular atom in the solid and
are more or less free to drift throughout the entire metal. They may be thought of as belonging
to the metal as a whole, or forming a “sea of electrons” or an “electron cloud.” The remaining
nonvalence electrons and atomic nuclei form what are called ion cores, which possess a net
positive charge equal in magnitude to the total valence electron charge per atom.
2.5 BONDING FORCES AND ENERGIES
Ionic Bonding
 The free electrons shield the positively charged ion cores from the mutually
repulsive electrostatic forces that they would otherwise exert upon one another;
consequently, the metallic bond is nondirectional in character. In addition, these
free electrons act as a “glue” to hold the ion cores together.
 Bonding may be weak or strong; energies range from 62 kJ/mol for mercury to
850 kJ/mol for tungsten. Their respective melting temperatures are 39C and
3414C (39F and 6177F).
 Metallic bonding is found in the periodic table for Group IA and IIA elements
and, in fact, for all elemental metals.
 Metals are good conductors of both electricity and heat as a consequence of
their free electrons.
 we note that at room temperature, most metals and their alloys fail in a ductile
manner—that is, fracture occurs after the materials have experienced significant
degrees of permanent deformation. This behavior is explained in terms of
deformation mechanism which is implicitly related to the characteristics of the
metallic bond.
2.7 SECONDARY BONDING OR
VAN DER WAALS BONDING
 Secondary bonds, or van der Waals (physical) bonds, are weak in comparison to the
primary or chemical bonds; bonding energies range between about 4 and 30 kJ/mol.
Secondary bonding exists between virtually all atoms or molecules, but its presence may
be obscured if any of the three primary bonding types is present. Secondary bonding is
evidenced for the inert gases, which have stable electron structures. In addition, secondary
(or intermolecular) bonds are possible between atoms or groups of atoms, which
themselves are joined together by primary (or intramolecular) ionic or covalent bonds.
Secondary bonding forces arise from atomic or molecular dipoles. In essence, an electric
dipole exists whenever there is some separation of positive and negative portions of an
atom or molecule.
2.7 SECONDARY BONDING OR
VAN DER WAALS BONDING
Fluctuating Induced Dipole Bonds
 A dipole may be created or induced in an atom or molecule that is normally
electrically symmetric—that is, the overall spatial distribution of the electrons is
symmetric with respect to the positively charged nucleus, as shown in Figure
2.21a. All atoms experience constant vibrational motion that can cause
instantaneous and short-lived distortions of this electrical symmetry for some of
the atoms or molecules and the creation of small electric dipoles. One of these
dipoles can in turn produce a displacement of the electron distribution of an
adjacent molecule or atom, which induces the second one also to become a
dipole that is then weakly attracted or bonded to the first (Figure 2.21b); this is
one type of van der Waals bonding. These attractive forces, which forces are
temporary and fluctuate with time, may exist between large numbers of atoms
or molecules.

The liquefaction and, in some cases, the solidification of the inert gases and other
electrically neutral and symmetric molecules such as H2 and Cl2 are realized because of
this type of bonding.
Fluctuating Induced Dipole Bonds
Polar Molecule–Induced Dipole Bonds
 Permanent dipole moments exist in some molecules by virtue of an
asymmetrical arrangement of positively and negatively charged regions; such
molecules are termed polar molecules.
Permanent Dipole Bonds
 Coulombic forces also exist between adjacent polar molecules as in Figure 2.20.
The associated bonding energies are significantly greater than for bonds
involving induced dipoles.
 The strongest secondary bonding type, the hydrogen bond, is a special case of
polar molecule bonding. It occurs between molecules in which hydrogen is
covalently bonded to fluorine (as in HF), oxygen (as in H2O), or nitrogen (as in
NH3). For each H-F, H-O, or H-N bond, the single hydrogen electron is shared
with the other atom. Thus, the hydrogen end of the bond is essentially a
positively charged bare proton unscreened by any electrons. This highly
positively charged end of the molecule is capable of a strong attractive force
with the negative end of an adjacent molecule, as demonstrated in Figure 2.23
for HF.
 The magnitude of the hydrogen bond is generally greater than that of the other
types of secondary bonds and may be as high as 51 kJ/mol, as shown in Table
2.3. Melting and boiling temperatures for hydrogen fluoride, ammonia, and
water are abnormally high in light of their low molecular weights, as a
consequence of hydrogen bonding.
Permanent Dipole Bonds