32 CHAPTER 2 .

Basic concepts: molecules

The Lewis structure for N2 shows that the N!N bond is

composed of three pairs of electrons and is a triple bond
(structures 2.3 and 2.4). Each N atom has one lone pair of
electrons. The Lewis structures 2.5 and 2.6 for O2 indicate
the presence of a double bond, with each O atom bearing
two lone pairs of electrons.

(2.3) (2.4)

Fig. 2.2 The structures of the homonuclear molecules (a) P4

(2.5) (2.6) and (b) S8.

Lewis structures give the connectivity of an atom in a tally by microwave spectroscopy or diffraction methods
molecule, the bond order and the number of lone pairs, and (see Chapter 4). It is convenient to define the covalent
these may be used to derive structures using the valence- radius, rcov , of an atom: for an atom X, rcov is half of the cova-
shell electron-pair repulsion model (see Section 2.8). lent bond length of a homonuclear X!X single bond. Thus,
rcov (S) can be determined from the solid state structure of
S8 (Fig. 2.2) determined by X-ray diffraction methods or,
2.2 Homonuclear diatomic molecules:
better still, by averaging the values of the bond distances of
valence bond (VB) theory S!S single bonds found for all the allotropes of sulfur.
Uses of the term homonuclear
For an atom X, the value of the single bond covalent radius,
The word homonuclear is used in two ways: rcov , is half of the internuclear separation in a homonuclear
X!X single bond.
. A homonuclear covalent bond is one formed between two
atoms of the same element, e.g. the H!H bond in H2 , the The a- and b-forms of sulfur (orthorhombic and
O¼O bond in O2 , and the O!O bond in H2 O2 (Fig. 2.1). monoclinic sulfur, respectively) both crystallize with S8
. A homonuclear molecule contains one type of element. molecules stacked in a regular arrangement. The packing
Homonuclear diatomic molecules include H2 , N2 and F2 , in the a-form (Fig. 2.3, density ¼ 2:07 g cm!3 ) is more
homonuclear triatomics include O3 (ozone) and examples efficient than that in the b-form (density ¼ 1:94 g cm!3 ).
of larger homonuclear molecules are P4 , S8 (Fig. 2.2) Van der Waals forces operate between the molecules, and
and C60 . half of the distance of closest approach of two sulfur
atoms belonging to different S8 rings is defined as the van
Covalent bond distance, covalent radius der Waals radius, rv , of sulfur. The weakness of the bonding
and van der Waals radius is evidenced by the fact that S8 vaporizes, retaining the ring
Three important definitions are needed before we discuss
covalent bonding.
The length of a covalent bond (bond distance), d, is the
internuclear separation and may be determined experimen-

Fig. 2.3 The packing of S8 rings in the a-allotrope of sulfur.

Fig. 2.1 The structure of hydrogen peroxide, H2 O2 ; O atoms The black box defines the unit cell (see Section 6.2). [Data:
are shown in red. S. J. Rettig et al. (1987) Acta Crystallogr., Sect. C, vol. 43, p. 2260.]
 Homonuclear diatomic molecules: valence bond (VB) theory 33

structure, without absorbing much energy. The van der minimum value when the internuclear separation, d, is
Waals radius of an element is necessarily larger than its 87 pm and this corresponds to an H!H bond dissociation
covalent radius, e.g. rv and rcov for S are 185 and 103 pm, energy, !U, of 303 kJ mol!1 . While these are near
respectively. Van der Waals forces include dispersion and enough to the experimental values of d ¼ 74 pm and
dipole–dipole interactions; dispersion forces are discussed !U ¼ 458 kJ mol!1 to suggest that the model has some
in the latter part of Section 6.13 and dipole moments in validity, they are far enough away from them to indicate
Section 2.6. Because van der Waals forces operate between that the expression for þ needs refining.
molecules, they are crucial in controlling the way in which
molecules pack in the solid state. Values of rv and rcov are The bond dissociation energy (!U) and enthalpy (!H) values
listed in Appendix 6. for H2 are defined for the process:
H2 ðgÞ !! 2HðgÞ
"

The van der Waals radius, rv , of an atom X is half of the

distance of closest approach of two non-bonded atoms
of X. Improvements to eq. 2.1 can be made by:
. allowing for the fact that each electron screens the other
The valence bond (VB) model from the nuclei to some extent;
of bonding in H2 . taking into account the possibility that both electrons 1
and 2 may be associated with either HA or HB , i.e. allow-
Valence bond theory considers the interactions between
ing for the transfer of one electron from one nuclear
separate atoms as they are brought together to form
centre to the other to form a pair of ions HA þ HB ! or
molecules. We begin by considering the formation of H2
HA ! HB þ .
from two H atoms, the nuclei of which are labelled HA
and HB , and the electrons of which are 1 and 2, respec- The latter modification is dealt with by writing two additional
tively. When the atoms are so far apart that there is no wavefunctions, 3 and 4 (one for each ionic form), and so
interaction between them, electron 1 is exclusively asso- eq. 2.1 can be rewritten in the form of eq. 2.3. The coefficient
ciated with HA , while electron 2 resides with nucleus HB . c indicates the relative contributions made by the two sets of
Let this state be described by a wavefunction 1 . wavefunctions. For a homonuclear diatomic such as H2 , the
When the H atoms are close together, we cannot tell which situations described by 1 and 2 are equally probable, as are
electron is associated with which nucleus since, although we those described by 3 and 4 .
gave them labels, the two nuclei are actually indistinguish-
þ ¼ N½ð 1 þ 2Þ þ cð 3 þ 4 Þ( ð2:3Þ
able, as are the two electrons. Thus, electron 2 could be
with HA and electron 1 with HB . Let this be described by Since the wavefunctions 1 and 2 arise from an inter-
the wavefunction 2 . nuclear interaction involving the sharing of electrons
Equation 2.1 gives an overall description of the covalently among nuclei, and 3 and 4 arise from electron transfer,
bonded H2 molecule; covalent is a linear combination of we can simplify eq. 2.3 to 2.4, in which the overall wave-
wavefunctions 1 and 2 . The equation contains a normali- function, molecule , is composed of covalent and ionic terms.
zation factor, N (see Box 1.3). In the general case where:
molecule ¼ N½ covalent þ ðc ) ionic Þ( ð2:4Þ
covalent ¼ c1 1 þ c2 2 þ c3 3 þ $$$
Based on this model of H2 , calculations with c * 0:25 give
1
N ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi values of 75 pm for d(H–H) and 398 kJ mol!1 for the bond
c1 þ c 2 þ c 3 2 þ $ $ $
2 2
dissociation energy. Modifying eq. 2.4 still further leads to
a value of !U very close to the experimental value, but
covalent ¼ þ ¼ Nð 1 þ 2Þ ð2:1Þ details of the procedure are beyond the scope of this book.†
Now consider the physical significance of eqs. 2.3 and
Another linear combination of 1 and 2 can be written as 2.4. The wavefunctions 1 and 2 represent the structures
shown in eq. 2.2. shown in 2.7 and 2.8, while 3 and 4 represent the ionic
! ¼ Nð 1 ! 2Þ ð2:2Þ forms 2.9 and 2.10. The notation HA (1) stands for ‘nucleus
HA with electron (1)’, and so on.
In terms of the spins of electrons 1 and 2, þ corresponds
to spin-pairing, and ! corresponds to parallel spins (non-
spin-paired). Calculations of the energies associated with
(2.7) (2.8) (2.9) (2.10)
these states as a function of the internuclear separation of
HA and HB show that, while ! represents a repulsive †
For detailed discussion, see: R. McWeeny (1979) Coulson’s Valence,
state (high energy), the energy curve for þ reaches a 3rd edn, Oxford University Press, Oxford.
34 CHAPTER 2 . Basic concepts: molecules

Dihydrogen is described as a resonance hybrid of these molecular orbital theory is fully consistent with O2 being a
contributing resonance or canonical structures. In the case diradical. When two N atoms ([He]2s2 2p3 ) combine to give
of H2 , an example of a homonuclear diatomic molecule N2 , an N+N triple bond results. Of the possible resonance
which is necessarily symmetrical, we simplify the picture structures, the predominant form is covalent and this
to 2.11. Each of structures 2.11a, 2.11b and 2.11c is a reso- gives a satisfactory picture of the bonding in N2 .
nance structure and the double-headed arrows indicate the
resonance between them. The contributions made by 2.11b In a diamagnetic species, all electrons are spin-paired; a
and 2.11c are equal. The term ‘resonance hybrid’ is diamagnetic substance is repelled by a magnetic field. A
paramagnetic species contains one or more unpaired electrons;
somewhat unfortunate but is too firmly established to be a paramagnetic substance is attracted by a magnetic field.
eradicated.

Self-study exercises
(2.11a) (2.11b) (2.11c)
1. Within VB theory, the wavefunction that describes the
bonding region between two H atoms in H2 can be writ-
The bonding in a molecule is described in terms of contributing ten in the form:
resonance structures. The resonance between these
contributing structures results in a resonance stabilization.
molecule =N[ covalent þ (c ) ionic)]
The relationship between resonance structures is indicated by
using a double-headed arrow.
Explain the meaning of this equation, including the
reason why the factor N is included.
A crucial point about resonance structures is that they do
not exist as separate species. Rather, they indicate extreme 2. It is incorrect to draw an equilibrium symbol between
bonding pictures, the combination of which gives a descrip- two resonance structures. The correct notation is a
tion of the molecule overall. In the case of H2 , the double-headed arrow. Explain why the distinction
contribution made by resonance structure 2.11a is signifi- between these notations is so important.
cantly greater than that of 2.11b or 2.11c. 3. Although O2 is paramagnetic, VB theory results in a
Notice that 2.11a describes the bonding in H2 in terms prediction that it is diamagnetic. Explain why this is
of a localized 2-centre 2-electron, 2c-2e, covalent bond. A the case.
particular resonance structure will always indicate a loca-
lized bonding picture, although the combination of several
resonance structures may result in the description of the
bonding in the species as a whole being delocalized (see
2.3 Homonuclear diatomic molecules:
Section 5.3). molecular orbital (MO) theory
An overview of the MO model
The valence bond (VB) model applied
to F2 , O2 and N2 In molecular orbital (MO) theory, we begin by placing the
nuclei of a given molecule in their equilibrium positions
Consider the formation of F2 . The ground state electronic
and then calculate the molecular orbitals (i.e. regions of
configuration of F is [He]2s2 2p5 , and the presence of the
space spread over the entire molecule) that a single electron
single unpaired electron indicates the formation of an F!F
might occupy. Each MO arises from interactions between
single bond. We can write down resonance structures 2.12
orbitals of atomic centres in the molecule, and such inter-
to describe the bonding in F2 , with the expectation that
actions are:
the covalent contribution will predominate.
. allowed if the symmetries of the atomic orbitals are
compatible with one another;
(2.12) . efficient if the region of overlap between the two atomic
orbitals is significant;
The formation of O2 involves the combination of two O atoms
. efficient if the atomic orbitals are relatively close in
with ground state electronic configurations of 1s2 2s2 2p4 .
energy.
Each O atom has two unpaired electrons and so VB theory
predicts the formation of an O¼O double bond. Since VB An important ground-rule of MO theory is that the number
theory works on the premise that electrons are paired wher- of MOs that can be formed must equal the number of
ever possible, the model predicts that O2 is diamagnetic. atomic orbitals of the constituent atoms.
One of the notable failures of VB theory is its inability to pre- Each MO has an associated energy and, to derive the
dict the observed paramagnetism of O2 . As we shall see, electronic ground state of a molecule, the available