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Ki2231
BASIC CONCEPTS OF Struktur dan
MOLECULES Kereaktifan
Anorganik

BONDING MODELS

§ Valence bond (VB) theory treats the formation of a

molecule as arising from the bringing together of complete
atoms which, when they interact, to a large extent
retain their original character.
§ Molecular orbital (MO) theory allocates electrons to
molecular orbitals formed by the overlap (interaction)
of atomic orbitals.

1
 pattern of bonds and lone pairs: it shows the number of the links, not the geometry of
the molecule. For example the BF4! ion is actually tetrahedral (2), not planar, and PF3 is
trigonal pyramidal (3).

2.2 Resonance
Key points: Resonance between Lewis structures lowers the calculated energy of 1/28/21
the molecule and
distributes the bonding character of electrons over the molecule; Lewis structures with similar energies
provide the greatest resonance stabilization.

A single Lewis structure is often an inadequate description of the molecule. The Lewis
structure of O3 (4), for instance, suggests incorrectly that one O!O bond is different from
the other, whereas in fact they have identical lengths (128 pm) intermediate between those
of typical single O!O and double O$O bonds (148 pm and 121 pm, respectively). This
deficiency of the Lewis description is overcome by introducing the concept of resonance,

Table 2.1 Lewis structures of some simple molecules*

LEWIS STRUCTURES
H H N N C O

§Lewis proposed that a covalent bond is O 3.1 Lewis Electron-Dot

S Diagrams | N
49
–
O O O O O O
formed when two neighbouring atoms share
2- 1+ 3- 1+ 1+ 1- 1+ 1- FIGURE 3.5 Resonance
an electron pair. C N O C N O C N O H
Structures of Fulminate, CNO - .
O
A B
N C S
§Lewis structures give the connectivity of an H H O O
EXERCISE 3.1 Use electron-dot diagrams and formal charges to predict the bond order
atom in a molecule,3 the4 bond3 order and the
for each bond in POF , SOF , and SO F -
.
3– 2– O –
numberSomeof lone pairs,
molecules and these
have satisfactory may
electron-dot be with octets but O
structures have more O
reasonable formal charge distributions in their structures with expanded electron
O Pcounts. O In O S O O Cl O
usedeachto ofderive
the cases structures
in Figure 3.6, the using the valence
actual molecules and ions are consistent with electron
O
counts greater than 8 on the central atom and with a large contribution from theO resonance O
shell structure
electron-pair repulsion
that uses multiple model
bonds to minimize (VSEPR)
formal charges. The multiple bonds may
also influence the shapes of the molecules. * Only representative resonance structures are given. Shapes are indicated only for
diatomic and triatomic molecules.

3.1.4 Multiple Bonds in Be and B Compounds

A few molecules—such as BeF2, BeCl2, and BF3—seem to require multiple bonds to sat-
isfy the octet rule for Be and B, even though multiple bonds for F and Cl are not generally
expected on the basis of the high electronegativities of these halogens. Structures minimiz-
3 ing formal charges for these molecules have only four electrons in the valence shell of Be
and six electrons in the valence shell of B, in both cases fewer than the usual octet. The
alternative, requiring eight electrons on the central atom, predicts multiple bonds, with
BeF2 analogous to CO2 and BF3 analogous to SO3 (Figure 3.7). These structures, however,
result in nonideal formal charges (2- on Be and 1+ on F in BeF2, and 1- on B and 1+
on the double-bonded F in BF3) on the basis of the usual rules.

Octet Expanded
Molecule Atom Formal Atom Formal Expanded
Charge Charge to:

SNF3 N S 2+ N S 0 12
N 2- N 0
F S F F S F

F F

SO2Cl2 O S 2+ O S 0 12
O 1- O 0
Cl S O Cl S O

Cl Cl

XeO3 Xe 3+ Xe 0 14
O O 1- O O 0
O Xe O O Xe O

SO32- S 1+ S 0 10
O O 1- O O 0,1-
O S O O S O

FIGURE 3.6 Formal Charge and Expanded Electron Counts on Central Atom.

2
 1/28/21

52 Chapter 3 | Simple Bonding Theory

Steric Number Geometry Examples Calculated Bond Angles

GEOMETRY 2 Linear CO2 180° O C O

MOLECULES BASED 3
Trigonal
SO3 120°
O
S
ON VSEPR THEORY
(triangular)
O O
H H
4 Tetrahedral CH4 109.5° C
H H
Cl
Trigonal Cl
5 PCl5 120°, 90° P Cl
bipyramidal
Cl
Cl
F
F F
6 Octahedral SF6 90° S
F F
F
F

F
Pentagonal F F
7 IF7 72°, 90° I
bipyramidal
3.2 Valence Shell Electron-Pair Repulsion | 53 F F

F
F F
F F
Square Ta
8 [TaF8]3− 70.5°, 99.6°, 109.5°
with experimental data. antiprismatic
F
se we are working with F F
F
roach will unlikely work FIGURE 3.8 VSEPR Predictions.

molecular structures are

5
45°

o a first approximation,
e treated similarly when
all shapes can be made
nd bonding pairs. These 45°
F
F
F X
X 70.5°
X
as in rationalizing why F
Ta
X
M 99.6°

l angle in methane and FIGURE 3.9 Conversion of a

F F X
109.5°
X
F F X X
Cube into a Square Antiprism.

n-pair repulsions involv- LONE-PAIR REPULSION

(bp) in the order
Although lone pairs do not contribute directly to the bonding, they do influence the shape of Mole
epulsions
the molecule and play an important role in its properties.
In this section we discu
ustrate the effect of lone H H 109.5° Valence bond theory 39 taken from both p- and
een carbon and each of isomerism are described
H C H C
far from each other as H
H
due to the presence of lone pairs. The Lewis structure of SF4 is shown in (13). The central S atom has
H
F
on, with all H i C i H H
four F atoms attached to it and one lone pair. The basic shape adopted by these five regions is trigonal F S F If two species have the s
bipyramidal. The potential energy is least if the lone pair occupies an equatorial site to give a molecular
F atom connectivity, but di
shape that resembles a see-saw, with the axial bonds forming the ‘plank’ of the see-saw and the equatorial
different atoms or groups
tom, but three are bond- H N H bonds the ‘pivot’. The S#F bonds then bend away from the lone pair (14).
N 13 SF4
bond, then the compound
H H
trogen. The nuclei form Self-test 2.3 Predict the shape of an XeF molecule.
H 2

H
cupies the fourth region 106.6°
F Stereoisomers fall int
n groups. Because each S
and enantiomers.
nuclei (H and N), these ValenceH O bond theory O
ms. The lone pair, on the The valence bond theoryH Diastereoisomers are ste
(VB theory) H Fig. 2.17
of bonding was the first quantum (a) The
mechanical theoryexperimentally determined structure of ClF3 and
bondingH (b) the rationalization
of atomic orbit- of this structure using the VSEPR model. of one another. Enantiom
cond nucleus to confine of to be developed. Valence bond theory considers the interaction
als on separate atoms as they 104.5°
are brought together to form a molecule. Although the com- mirror-images of one an
pread out and to occupy putational techniques involved have been largely superseded by [TeF molecular!orbital theory,
7 ] ,andtheareTe–F
used ax
bond distance is 179 pm and the Te–Feq
, the H i N i H angles much of the language and some of the concepts of VB theory still remain
FIGURE 3.10 Shapes of
throughout chemistry. distances lie in the range 183 to 190 pm.
14 SF4
In this section, we shall
Methane, Ammonia, and Water. isomers. We return to en
6 Among species in which the VSEPR model appears to fail
two lone pairs and two 2.4 The hydrogen molecule
are [SeCl6 ]2! , [TeCl6 ]2! and [BrF6 ]! (see also Section 16.7).
arly tetrahedral arrange- Key points: In valence bond theory, the wavefunction of an electron pair is formed by superimposing
When
the wavefunctions for the separated fragments of the molecule; a molecular characterized
potential energy curve as alkali metal salts, these anions are Square planar speci
pulsion, between the two shows the variation of the molecular energy with internuclear separation. found to possess regular octahedral structures in the solid
pair (lp–bp) repulsion is The two-electron wavefunction for two widely separated H atomsstate, is ! ! " whereas
(1)" (2), where
In a square planar specie
the VSEPR model suggests shapes based on
F on atoms A and B. (Although ", chi, is also used for electronega- the four Cl 3 atoms
A B

a result, the H i O i H tivity,

" and " are H1s orbitals
A B
the context makes it unlikely that the two usages will be confused: " is commonly electron pairs around the central atom.
there being seven
angles. The net result is used to denote anFatomicSorbital in computational chemistry.) When the atoms are close, it [PtCl3 (PMe3 )]! (2.31),
Although these structures cannot readily be predicted, we
is not possible to know whether it is electron 1 that is on A or electron 2. An equally valid
F
re space to lone electron description is therefore ! ! " (2)" (1), in which electron 2 is on can ment of the groups aro
A B
A andrationalize
electron 1 is on them
B. in terms of having a stereochemically
nce they are attracted to When two outcomes are F equally probable, quantum mechanics instructs us to describe the (The use of arrows or li
inactive pair
true state of the system as a superposition of the wavefunctions for each possibility, so a of electrons. Stereochemically inactive lone
Equatorial
better description lone pair
of the molecule than either wavefunction alone pairs
is the linear
compounds is discussed
are combination
usually observed for the heaviest members of a per-
 1/28/21

SOME SPECIES THE VSEPR FAILS TO PREDICT

[SeCl6]2-, [TeCl6]2- and [BrF6]- are found to possess octahedral structures,

despite having seven electron pairs around the central atom.
These can be rationalized in terms of having a stereochemically inactive
pair of electrons.
Stereochemically inactive lone pairs are usually observed for the heaviest
members of a periodic group, and the tendency for valence shell s
electrons to adopt a non-bonding role in a molecule is called the stereo-
chemical inert pair effect.
[SbCl6]- and SbCl6]3- ions are also octahedral.

7
36 2 Molecular structure and bonding

36 2 Molecular structure and bonding

in which the actual structure of the molecule is taken to be
all the feasible Lewis structures corresponding to a given a
Resonance is indicated by a double-headed arrow, as in
in which the actual structure of the molecule is taken
RESONANCE STRUCTURES O
allOthe feasible Lewis
O
O O structures
O corresponding to a giv
Resonance is indicated by a double-headed arrow, a
§A single Lewis structure is often an inadequate At this stage we are not indicating the shape of the mole
description of the molecule. tured as O O
a blending of structures, not a flickering alternat
§Resonance; the actual structure of the molecule is O
mechanical O
terms, O
the electron O
distribution of each structur
taken to be a superposition, or average, of all the tion, and the actual wavefunction, !, of the molecule is the
feasible Lewis structures corresponding to a given wavefunctions
At this stage for
we each contributing
are not indicatingstructure:1
the shape of the m
atomic arrangement.
tured as a blending
! ! !(O"O!O) # of structures, not a flickering alte
!(O!O"O)
§Resonance between Lewis structures lowers the
calculated energy of the molecule and distributes the mechanical terms, the electron distribution of each str
The overall wavefunction is written as a superposition with
bonding character of electrons over the molecule tion, and the actual wavefunction, !, of the molecule i
structures because the two structures have identical1 energie
§The Lewis structure of O3, suggests incorrectly that one wavefunctions for each contributing structure:
or more Lewis structures is called a resonance hybrid. Note
O-O bond is different from the other, in fact they have structures that differ only
! ! !(O"O!O) in the allocation of electrons; res
# !(O!O"O)
identical lengths (128 pm) intermediate between those structures in which the atoms themselves lie in different po
of typical single O-O (148 pm) and double O=O bonds The overall wavefunction is written
resonance between the structures SOO as a OSO.
and superposition
(121 pm). structures
Resonancebecause
has twothe twoeffects:
main structures have identical en
or more Lewis structures is called a resonance hybrid.
1. Resonance averages the bond characteristics over the m
structures that differ only in the allocation of electron
2.structures
The energy of a resonance
in which hybrid
the atoms structurelie
themselves is in
lower than
differen
8 structure.
resonance between the structures SOO and OSO.
TheResonance
energy of the
hasOtwo
3
resonance hybrid, for instance, is low
main effects:
structure alone. Resonance is most important when there a
1. Resonance
energy averages
that can be writtenthe bond characteristics
to describe the molecule, over
as fort
tures of the same energy contribute equally to the 4
2. The energy of a resonance hybrid structure is lowers
overall
Structures
structure.with different energies may also contribute
but, in general, the greater the energy difference between tw
Thecontribution
the energy of the
of Otheresonance hybrid, for instance, is
3 higher energy structure. The BF
structure alone. Resonance is most
be regarded as a resonance hybrid of important when
the structures th
show
 wavefunctions for each contributing structure:1
! ! !(O"O!O) # !(O!O"O)
The overall wavefunction is written as a superposition with equal contributions from both
structures because the two structures have identical energies. The blended structure of two
or more Lewis structures is called a resonance hybrid. Note that resonance occurs between
structures that differ only in the allocation of electrons; resonance does not occur between
structures in which the atoms themselves lie in different positions. For instance, there is no
1/28/21
resonance between the structures SOO and OSO.
Resonance has two main effects:
1. Resonance averages the bond characteristics over the molecule.
2. The energy of a resonance hybrid structure is lower than that of any single contributing
structure.
The energy of the O3 resonance hybrid, for instance, is lower than that of either individual
structure alone. Resonance is most important when there are several structures of identical
energy that can be written to describe the molecule, as for O3. In such cases, all the struc-
tures of the same energy contribute equally to the overall structure.
Structures with different energies may also contribute to an overall resonance hybrid
EXAMPLES OF RESONANCE but, in general, the greater the energy difference between two Lewis structures, the smaller

STRUCTURES
the contribution of the higher energy structure. The BF3 molecule, for instance, could
be regarded as a resonance hybrid of the structures shown in (5), but the first structure
dominates even though the octet is incomplete. Consequently, BF3 is regarded primarily
as having that structure with a small admixture of double-bond character. In contrast, for
the NO3" ion (6), the last three structures dominate, and we treat the ion as having partial
The BF3 molecule could be double-bond character.

regarded as a resonance F F F F
cular structure and bonding
hybrid of the structures shown B B B B
in (5), but the first structure F
orbital formed by interference, or ‘mixing’, between the A2s and the A2p orbitals. The ori-
F F F F F F F
5 BF3
dominates
gin of the hybridization even
can be appreciated though
by thinking the
of the four atomic orbitals, which

octet is incomplete.
are waves centred on a nucleus, as being like ripples spreading from a single point on the
surface of a lake: the waves interfere destructively and constructively in different regions, – – – –
and give rise to four new shapes. O O O O
In contrast, for the NO3 ion - hybrid orbitals are
The specific linear combinations that give rise to four equivalent
N N N N
O O O O O O O O
(6), the last three structures
h1 ! s " px " py " pz h2 ! s # px # py " pz
(2.2)
6 NO3–
3 x
dominate, and we treat the ion
h !s#p "p #p h !s"p #p #p
y z 4 x y z

as having partial double-bond

As a result of the interference between the component orbitals, each hybrid orbital con-
sists of a large lobe pointing in the direction of one corner of a regular tetrahedron and a
in the opposite direction (Fig. 2.7). The angle between2.3
character.
smaller lobe pointing the The VSEPR model
axes of
our equivalent sp3
the hybrid orbitals is the tetrahedral angle, 109.47°. Because each hybrid is built from one
one points towards a
s orbital and three p orbitals, it is called an sp3 hybrid orbital. There is no simple method for predicting the numerical value of bond angles even in
egular tetrahedron.
It is now easy to see how the VB description of a CH4 molecule is consistentsimple molecules, except where the shape is governed by symmetry. However, the valence
with a tetra-
hedral shape with four equivalent C#H bonds. Each hybrid orbital of the promoted carbon
atom contains a single unpaired electron; an electron in !H1s can pair with each1one, giving
This wavefunction is not normalized (Section 1.5). We shall often omit normalization constants from
9rise to a $ bond pointing in a tetrahedral direction. Because each sp3 hybridlinear
orbital has
combinations in order to clarify their structure. The wavefunctions themselves are formulated in the
the same composition, all four $ bonds are identical apart from their orientation in space.
valence bond theory, which is described later.
A further feature of hybridization is that a hybrid orbital has pronounced directional
character, in the sense that it has enhanced amplitude in the internuclear region. This di-
rectional character arises from the constructive interference between the s orbital and the
positive lobes of the p orbitals. As a result of the enhanced amplitude in the internuclear
region, the bond strength is greater than for an s or p orbital alone. This increased bond
strength is another factor that helps to repay the promotion energy.
Hybrid orbitals of different compositions are used to match different molecular ge-
ometries and to provide a basis for their VB description. For example, sp2 hybridization is
used to reproduce the electron distribution needed for trigonal-planar species, such as on

HYBRIDIZATION OF ATOMIC ORBITALS

B in BF3 and N in NO3#, and sp hybridization reproduces a linear distribution. Table 2.4
gives the hybrids needed to match the geometries of a variety of electron distributions.

Table 2.4 Some hybridization schemes

Coordination number Arrangement Composition

2 Linear sp, pd, sd
Angular sd
3 Trigonal planar sp2, p2d
Unsymmetrical planar spd
Trigonal pyramidal pd2
4 Tetrahedral sp3, sd3
Irregular tetrahedral spd2, p3d, pd3
Square planar p2d2, sp2d
5 Trigonal bipyramidal sp3d, spd3
Tetragonal pyramidal sp2d2, sd4, pd4, p3d2
Pentagonal planar p2d3
6 Octahedral sp3d2
Trigonal prismatic spd4, pd5
Trigonal antiprismatic p3d3

Molecular orbital theory

We have seen that VB theory provides a reasonable description of bonding in simple mole-
cules. However, it does not handle polyatomic molecules very elegantly. Molecular orbital
theory (MO theory) is a more sophisticated model of bonding that can be applied equally
successfully to simple and complex molecules. In MO theory, we generalize the atomic

10

5
 1/28/21

40 2 Molecular structure and bonding

VB MODEL OF BONDING IN H2 to a strong

of the curv
bonded tog
HA(1)HB(2) HA(2)HB(1) HA(1,2) -HB+ HA+HB (1,2)- Internuclear rises as the
y1 y2 y3 y4 Re separation
of the stiffn
0
(Section 8.4

Energy
ycov = y+ = N (y1 + y2) (spin pairing), and
y- = N (y1 - y2) (parallel spins) 2.5 Hom
Energy of y+ reaches a minimum value when the internuclear Key point: E
separation, d, is 87 pm and this corresponds to an H-H bond form ! and "
dissociation energy, D, of 303 kJ/mol.
De A similar d
the experimental values of d = 74 pm and D = 458 kJ/mol.
ering homo
Fig. 2.3 A molecular potential energy curve
If the contribution of y3 and y4 is included, then showing how the total energy of a molecule
to the same
varies as the internuclear separation is
we conside
y+ = N [(y1 + y2) + c (y3 + y4)] or y+ = N [ycovalent + (c´ yionic)] changed. know to be
so we can
Based on this model of H2, calculations with c = 0.25 give values the other a
of 75 pm for d(H–H) and 398 kJ/mol for the bond dissociation formed by
energy. wavefuncti
simple way
nuclear axi
11 The rema
symmetry a
A " bond a
side (Fig. 2.
Fig. 2.4 The formation of a " bond. bles a pair o
of orbital a
" bond is t
the signs (a
bond is clas
VB MODEL OF BONDING IN H 2 There are
als and the
pattern in N
Physical significant of the structur
has cylindr
y+ = N [(y1 + y2) + c (y3 + y4)] or y+ = N [ycovalent + (c´ yionic)] " bonds fo

H2 can be described as resonance hybrid of 3 structures

2.6 Polya
H-H « H+ H- « H- H+ Key points:
The bonding in a molecule is described in terms of contributingFig.resonance
2.5 The VB description of N2. Two
neighbouring
structures. The resonance between these contributing structures results
electrons inbond
form a ! a and another are formed b
resonance stabilization. two pairs form two " bonds. In linear
molecules, where the x- and y-axes are not To introduc
A crucial point about resonance structures is that they do not exist
specified,asthe electron density of " bonds electron co
separate species. Rather, they indicate extreme bonding pictures, the symmetrical around the
is cylindrically The two un
combination of which gives a description of the molecule overall.
internuclear axis. orbital, and
cal symmet
For H2 the contribution of covalent structure is significantly greater that that als lie at 90
of ionic structures. predict, the
predicts a b
the structur
configuratio
12 by spin pair
dicular to e
An NH3 mo
Another
tetravalenc

6
 1/28/21

AN OVERVIEW OF THE MO MODEL

Place the nuclei of a given molecule in their equilibrium positions and then
calculate the molecular orbitals. Homonuclear diatomic molecules: molecular orbital (MO) theory

MO is region of space spread over the entire molecule that a single electron might
occupy. are placed, according to the aufbau principle, in
electrons
MOs beginning with that of lowest energy. The sum of
Each
the MO arises
individual from interactions
energies between
of the electrons in theorbitals
orbitals of atomic centers in the
molecule, and such interactions are:
(after correction for electron–electron interactions) gives
. allowed
the if theofsymmetries
total energy of the atomic orbitals are compatible with one another;
the molecule.
. efficient iforbital
Molecular the region of overlap
theory appliedbetween the two atomic orbitals is significant;
to the bonding
in H2
. efficient if the atomic orbitals are relatively close in energy.
An approximate description of the MOs in H2 can be
obtained by considering them as linear combinations of
atomic orbitals (LCAOs). Each of the H atoms has one 1s
atomic orbital; let the two associated wavefunctions be 1
Fig. 2.4 An orbital interaction diagram for the formation of H
13 and 2 . In36Section
CHAPTER 2 1.6, we mentioned
. Basic concepts: molecules the importance of two hydrogen atoms. By the aufbau principle, the two electron
the signs of the wavefunctions with respect to their overlap occupy the lowest energy (bonding) molecular orbital.
T H E O RY
during bond formation. The sign of the wavefunction
Box 2.1 The parity of MOs for a molecule that possesses a centre of inversion
associated with the 1s atomic orbital may
We consider symmetry in Chapter 3, but it is useful at this
be either þ
then the orbital is labelled u (from the word we ungerade,construct the orbital interaction diagram first an
or ". Just aspoint transverse waves interfere
to consider the labels that are commonly used to describe
the parity of a molecular orbital. A homonuclear diatomic
German for ‘odd’). For example, the !-bonding MO in H
in a
(Fig. 2.5a) is constructive put
labelled ! , while the antibonding MO
!
g
2

in the electrons according to the aufbau principle

molecule (e.g. H , Cl ) possesses a centre of inversion
2 2 (Fig. 2.5b) is ! . u
(in-phase) or(centre
destructive
of symmetry), and the (out-of-phase)
parity of an MO describes the
way in which the orbital behaves with respect to this centre
manner,
Parity labels onlyso too
apply to MOs indo
molecules that possess a
The bonding and antibonding MOs in H2 are giv
centre of inversion (centrosymmetric molecules), e.g. homo-
orbitals. Mathematically,
of inversion.
we represent the possible combi-
nuclear X , octahedral EX and square planar EX molecules.
2 6
labels ! and !# (‘sigma’ and ‘sigma-sta
4

MO of OF H symmetry
First find the centre of inversion in the molecule; this is Heteronuclear XY, or tetrahedral EX molecules, 4 for

lines2
the point through which you can draw an infinite number of example, do not possess a centre of inversion and are called
nations the two
straight such1s atomic
that each orbitals
line passes through a pair of similarbynon-centrosymmetric
eqs. 2.5 species. and 2.6, more fully, !g ð1sÞ and !u # ð1sÞ to indicate their a
points, one on each side of the centre of symmetry and at equal
# it:
where N and Nfrom
distances are the normalization Self-study factors. Whereas
exercises orbital origins and the parity of the MOs (see Box 2
#
the
MO MOs in H2 can
is an in-phase (bonding)be obtained interaction, by
Look atconsidering is an
MO2.7 which
Fig.
out- them
may be applied to order
the MOs astolinear
in the definecombinations
these labels, consider the pictorial rep
of atomic orbitals (LCAOs).
homonuclear diatomic O .
of-phase (antibonding) interaction. 2

tations of the two MOs. Figure 2.5a shows that when

Homonuclear diatomic molecules: molecular orbital (MO) theory
1. Why does a !-MO formed by the overlap of two 2p
(Fig. 2.7a) have the label ! ? g
orbitals z
35
MOðin-phaseÞ ¼ ¼ N½ 1þ 2(
MO ð2:5Þ
2. Why does a "-MO formed by the overlap of two 2px orbitals atomic orbitals interact in phase, the two wavefun
(Fig. 2.7c) have the label "u?
Now ask the question: ‘Does the wavefunction have the same
electrons are placed, according sign at the same
to# the aufbau
distance but in#opposite
principle, in3. Figs.
directions from the The antibonding MOs shown at the right-handreinforcesides of each other, especially in the region of
centre¼ of symmetry?’ ¼ N ½
1 " 2( ð2:6Þ
! !
MOðout-of-phaseÞ MO u 2.7b and 2.7d carry the labels
g ! and " , respectively.
MOs beginning with thattheIfof lowest energy. The
the answer is ‘yes’, then the orbital is labelled g (from
word gerade, German for ‘even’). If the answer is ‘no’,
sum of Explain the difference in the parity labels. between the nuclei. The two electrons occupying thi
the individual energies of N the electrons # in the orbitals will be found predominantly between the two nucle
The values
N =forN*electron–electron = (½)0.5 of and N are determined using eqs. 2.7 and
(after correction
2.8 where S is the overlap integral. This is a measure interactions) gives the build-up of electron density reduces internuclear
the total energy of the molecule. sion. Figure 2.5b illustrates that the out-of-phase inter
of the extent to which the regions of space described by
the two wavefunctions
Molecular orbital theory applied to1 the bonding and 2 coincide. Although we results in a nodal plane between the two H nuclei.
in H2 mentioned earlier that orbital interaction is efficient if the antibonding orbital were to be occupied, there woul
region of overlap between the two atomic orbitals is signifi- zero probability of finding the electrons at any po
An approximate description of the MOs in H2 can be
cant, the numerical value of S is still much less than unity the nodal plane. This lack of electron density rais
obtained by considering them as linear combinations of
and is often
atomic orbitals (LCAOs). Each of the H atoms has one 1s neglected giving the approximate results internuclear repulsion and, as a result, destabilizes th
shown in eqs.
atomic orbital; let the two associated wavefunctions be 1 2.7 and 2.8. Now let us return to the ! and !# labels. An M
Fig. 2.4 An orbital interaction !-symmetry diagram foriftheitformation of H2 from with respect to
is symmetrical
and 2 . In Section 1.6,1 we mentioned 1 the importance of two hydrogen atoms. By the aufbau principle, the two electrons
N ¼ p ffi ffi ffi ffi ffiffi ffi ffi ffi ffi
the signs of the wavefunctions with respect to their overlap ffi ffi ffi ffi ffi ffi ffi ) p ffi ffi ð2:7Þ
occupy the lowest energyjoining (bonding) the twoorbital.
molecular nuclei; i.e. if you rotate the o
14 2ð1 Fig. þThe SÞ sign 2 of the
during bond formation. 2.5 Schematic grepresentations of (a) the wavefunction
u
!
about
bonding (! ) and (b) the antibonding (! ) molecular orbitals in the H molecule. The H nuclei
2 the internuclear axis (the axis joining the two n
represented by black dots. The red orbital lobes could equally well be marked with a þ sign, and the blue lobes with a # sign (or vice
associated with 1are 1of the wavefunction. be þ of we
N # ¼thep1s ffiatomic ffiffiffiffiffiffi ’04,)orbital
pffiffi may
versa) to indicate the sign (c) Moreeither
realistic representations the molecular orbitals of H , generated computationally
ffiffiffiffiffiffiusing ffiffiffiffiSpartan #Wavefunction Inc. 2003.
2
construct ð2:8Þ the orbital centres marked
interaction in Figs.
diagram first2.5a and 2.5b), there is no
and then
or ". Just as transverse 2ð1 waves " SÞ interfere 2 in a constructive put in the electrons according to # aufbau principle.
the
change. A ! -orbital must exhibit two properties:
(in-phase) or destructive (out-of-phase) manner, so too do The bonding and antibonding MOs in H2 are given the
The interaction between thethe possible
H 1s atomic
combi-orbitals on forming . the
orbitals. Mathematically, we represent symmetry labels ! and ! label means
!# (‘sigma’ that rotation
and ‘sigma-star’) 7 abo
or, of the orbital
H2two
nations of the may be represented
1s atomic orbitals by by
eqs.the
2.5 energy
and 2.6, level diagram in #
more fully, !g ð1sÞ andinternuclear axis generates
!u ð1sÞ to indicate no phase change, and
their atomic
where N and N #2.4.
Fig. are The
the normalization
bonding MO,factors. MO , Whereas
is stabilizedorbital
withorigins
respectand the. parity
the #
label
of the means
MOs that
(see Boxthere isIna nodal plane betwe
2.1).
# #
MO is an in-phase
to the 1s(bonding)
atomic interaction,
orbitals, while is anantibonding
MO the out- orderMO,
to define ,
MOthese labels, consider the plane
pictorial represen- to the internuclea
nuclei, and this is orthogonal
of-phase (antibonding) interaction.
is destabilized. †
Each H atom contributes onetations electron and,
of the two MOs. Figure 2.5a shows that when the 1s
The ground state electronic configuration of H may b
 1/28/21

OVERLAP OF TWO P-ORBITALS

38 CHAPTER 2 . Basic concepts: molecules
38 CHAPTER 2 . Basic concepts: molecules

Fig. 2.7 The overlap of two 2p atomic orbitals for which the atomic nuclei are defined to lie on the z axis: (a) direct overlap along the z axis
gives a !g ð2pz Þ MO (bonding); (b) the formation of the !u ! ð2pz Þ MO (antibonding); (c) sideways overlap of two 2px atomic orbitals gives a
15 " ð2p Þ MO (bonding); (d) the formation of " ! ð2p Þ MO (antibonding). Atomic nuclei are marked in black and nodal planes in grey. The
u
Fig. x
2.7 The overlap of two 2p atomic orbitals g
forxwhich the atomic
diagrams on the right-hand side are more realistic representations
nuclei are defined to lie on the z axis: (a) direct overlap along the z axis
of the MOs and have been generated computationally using Spartan ’04,
gives a !g ð2pz Þ MO
#Wavefunction (bonding);
Inc. 2003. (b) the formation of the !u ! ð2pz Þ MO (antibonding); (c) sideways overlap of two 2px atomic orbitals gives a
!
"u ð2px Þ MO (bonding); (d) the formation of "g ð2px Þ MO (antibonding). Atomic nuclei are marked in black and nodal planes in grey. The
diagrams
orbitals.onAnthe orbital
right-hand side are more
interaction realistic
diagram representations
similar of the The
to that for MOs and have been
bonding in generated
F2 and O computationally
2
using Spartan ’04,
Li (Fig. 2.6b)Inc.
#Wavefunction
2
2003.
is appropriate. The difference between Li 2
The valence shell of an F atom contains 2s and 2p atomic
and Be is that Be has two more electrons than Li and
2
orbitals. An orbital2 interaction diagram similar to that
these occupy the !! ð2sÞ MO. The predicted bond order in
2
for The bonding
orbitals, and the in F2 and of
formation O2an F2 molecule involves
LiBe
2 2(Fig. 2.6b) is appropriate. Theprediction
differenceisbetween Li2 2s$2s and 2p–2p orbital interactions. Before we can
is thus zero. In practice, this essentially The valence shelldiagram
of an Ffor
atom
and Be2 isalthough
that Be2 there
has two more electrons construct an MO thecontains
formation 2s and
of F2p atomic
2 , we
fulfilled, is evidence for anthan Li2 and
extremely orbitals, and what
the formation
must consider types of of an F2 molecule
interactions involves
are possible
these
unstableoccupy
Be2 the !! ð2sÞ
species MO.
with Thelength
bond predicted bond
245 pm andorder
bondin
2s$2s pand
between 2p–2p
atomic orbital interactions. Before we can
orbitals.
Be 2 is thus
energy mol$1In. practice, this prediction is essentially
10 kJzero.
By convention,
construct an MOeach p atomic
diagram fororbital is directedofalong
the formation F2 , we
fulfilled, although there is evidence for an extremely one of the three Cartesian axes (Fig. 1.10), and, in are
consider-
must consider what types of interactions possible
unstable
A basis set 2 species
Beof orbitals iswith bondoflength
composed 245 pm
those which and bond
are available

HOMONUCLEAR DIATOMIC MOLECULES

ing the formation
between of aorbitals.
p atomic diatomic X2 , it is convenient to fix the
for orbital
energy mol$1 .
10 kJinteractions. positions of the X nuclei on one of the axes. In diagram 2.13,
In each of Li2 and Be2 , it is unnecessary to include the
By convention, 5.2on
the nuclei are placed Homonuclear
each p atomic orbital Diatomic
of axis is Molecules
is directed along
the z axis, but this choice | 125
one of the three Cartesian axes (Fig. 1.10), and, in consider-
A basis
core (1s)setatomic
of orbitals is composed
orbitals in order ofto those
obtainwhich are available
a useful bonding arbitrary. Defining these positions also defines the relative
ing the formation
orientations of asets
of the two diatomic X2 , it is(Fig.
of p orbitals convenient
2.7). to fix the
for orbitalThis
picture. interactions.
is true more generally, and throughout positions of the X nuclei on one of the axes. In diagram 2.13,
*
this book, MO treatments of bonding focus *
s on the
only FIGURE 5.6 Interaction
sinteractions to uthe the nuclei are placed on the z axis, but this choice of axis is
positions alsobetween
defines the Molecular Orbitals.
uIn each of between
Li2 and Be the2 , valence
it is unnecessary
orbitals of include
atomsthe
core (1s) atomic orbitals in order to obtain a useful bonding
concerned.
arbitrary. Defining these(2.13) relative
picture. This is true more generally, and throughout orientations of the two sets of p orbitalsMixing molecular orbitals of
(Fig. 2.7).
*pbook,
pgthis * MO treatments of bonding focus
pg*only
pg*on the the same symmetry results in
g
interactions between the valence orbitals of the atoms a greater energy difference
concerned. (2.13) between the orbitals. The s
orbitals mix strongly; the s*
2p 2p 2p 2p orbitals differ more in energy
sg and mix weakly.

pu pu pu pu

sg

su* su*

2s 2s 2s 2s
sg
sg

No mixing Mixing of sg orbitals

(a) (b)

16
interact to lower the energy of the sg 12s2 and to raise the energy of the sg 12p2 as shown
in Figure 5.6(b). Similarly, the su* 12s2 and su * 12p2 orbitals interact to lower the energy
of the su * 12s2 and to raise the energy of the su * 12p2. This phenomenon is called mix-
ing, which takes into account that molecular orbitals with similar energies interact if they
have appropriate symmetry, a factor ignored in Figure 5.5. When two molecular orbitals 8
of the same symmetry mix, the one with higher energy moves still higher in energy, and
the one with lower energy moves lower. Mixing results in additional electron stabilization,
and enhances the bonding.
A perhaps more rigorous approach to explain mixing considers that the four s molecu-
lar orbitals (MOs) result from combining the four atomic orbitals (two 2s and two 2pz) that
 to the antibonding orbital. The dissociation energy of H2 is 4.5 eV (434 kJ mol!1), which
gives an indication of the location of the bonding orbital relative to the separated atoms.
The Pauli exclusion principle limits to two the number of electrons that can occupy
N2+
any molecular orbital and requires that those two electrons be paired (↑↓). The exclusion

Energy
principle is the origin of the importance of the pairing of the electrons in bond formation
in MO theory just as it is in VB theory: in the context of MO theory, two is the maximum
number of electrons that can occupy an orbital that contributes to the stability of the mol-
N2 1/28/21
2σg I = 15.6 eV
ecule. The H2 molecule, for example, has a lower energy than that of the separated atoms
because two electrons can occupy the orbital !" and both can contribute to the lowering
of its energy (as shown in Fig. 2.10). A weaker bond can be expected if only one electron is 1πu I = 16.7 eV
present in a bonding orbital, but nevertheless H2" is known as a transient gas-phase ion; its
dissociation energy is 2.6 eV (250.9 kJ mol!1). Three electrons (as in H2!) are less effective
than two electrons because the third electron must occupy the antibonding orbital !! and
hence destabilize the molecule. With four electrons, the antibonding effect of two electrons
in !! overcomes the bonding effect of two electrons in !". There is then no net bonding. It 1σu I = 18.8 eV
follows that a four-electron molecule with only 1s orbitals available for bond formation,
such as He2, is not expected to be stable relative to dissociation into its atoms.
So far, we have discussed interactions of atomic orbitals that give rise to molecular
Fig. 2.11 The UV photoelectron spectrum of
MIXING AND NON-MIXING ORBITALS
orbitals that are lower in energy (bonding) and higher in energy (antibonding) than the
47 Molecular
separated atoms. In addition, it is possible to generate orbital orbital
a molecular theory that has the
N2. The fine structure in the spectrum arises
from excitation of vibrations in the cation
same energy as the initial atomic orbitals. In this case, occupation of this orbital neither formed by photoejection of an electron.
stabilizes nor destabilizes the molecule and so it is described as a nonbonding orbital. Typi-
Li2 Be2 B2 C2 cally,
N2 a nonbonding
O2 orbital
F2 is a molecular orbital that consists of2σa single orbital on one
atom, perhaps because there is no atomic orbital of the correct symmetryu for it to overlap 2σu

u
on a neighbouring atom. 1πg 1πg
If the 2s and 2p energy are 2σ
close,
2.8 Homonuclear diatomic molecules
u

g Mixing between then occur,

Although the structures of diatomic molecules can be2pcalculated effortlessly by2p
using com-
2p 2p

as in themercial
casesoftware
of Npackages,
2 molecule.
the validity of any such calculations must, at some point, be
2σ
confirmed by experimental data.
1πg Moreover, elucidation of molecular g
structure can often

Energy
1πu
Energy
be achieved by drawing on experimental information. One of the most 1πu direct portrayals of
g electronic structure is obtained from ultraviolet photoelectron spectroscopy (UPS, Section 2σg
8.8) in which electrons are ejected from the orbitals they occupy in molecules and their
u
energies determined. Because1πthe peaks in a photoelectron spectrum 1σu
u 1σu correspond to the
various kinetic energies 126
of photoelectrons ejectedOrbitals
Chapter 5 | Molecular from different orbitals of the molecule,
2s 2s
the spectrum gives a vivid portrayal
2σg of the molecular 2sorbital energy levels of2s a molecule
(Fig. 2.11). 1σg
u
on the basis of s@p
1σmixing, gain either a slightly bonding or slightly antibonding character
g
and contribute in minor ways to the bonding. Each orbital must be considered separately
(a) The orbitals on the basis of its energy and electron distribution.
1σu
Key points: Molecular orbitals are classified as #, $, or % according to their rotational symmetry about
g the internuclear axis, and (in centrosymmetric species) as g orDiatomic5.2.3
u accordingMolecules of thewith
to their symmetry First andFig.Second
2.12 The Periods
molecular orbital energy level
respect to inversion. Fig.Before
2.18 The
proceeding
molecularwith examples
orbital of homonuclear
energy level diatomic
diagram molecules,
for the we2 must
later Period define
homonuclear
two types
diagram of magnetic
for Period behavior,
2 homonuclear and diamagnetic
paramagnetic diatomic
diatomic molecules.. This
Paramagnetic com-be
diagram should
1σg
Our task is to see how MO theory can account molecules forpounds are attracted
from
the featuresLi2 to N2. by an
revealed by external magnetic field.
photoelectron usedThis
for Oattraction
2
and F2. is a consequence of
one or more unpaired
spectroscopy and the other techniques, principally absorption spectroscopy, that are used electrons behaving as tiny magnets. Diamagnetic compounds, on
17 The variation of orbital energies for Period 2 homonuclear diatomic molecules
to study diatomic molecules.fromWeLi2 are
to F2concerned
. the other hand,
predominantly haveouter-shell
with no unpaired electrons
valence or-and are repelled slightly by magnetic fields.
(An experimental measure of the magnetism of compounds is the magnetic moment, a
bitals, rather than core orbitals. As with H2, the starting point in the theoretical discussion
e building-up principle 17for molecules concept developed in Chapter 10 in the discussion of the smagnetic properties
is the minimal basis set, the smallest set of atomic orbitals from which useful molecular s of coordina-
tion compounds.)
orbitals can be built. In Period 2 diatomic molecules, the minimal basis set consists of the
H2, He2, and the homonuclear diatomic species shown in Figure 5.7 will now be
ints: The building-up principle is used to predict the ground-state electron configurations by
one valence s orbital and three valence p orbitals on each atom,
discussed. giving eight
As previously atomic atomic
discussed, orbit- orbital energies decrease across a row in
modating electrons in the array of molecular orbitals summarized in Fig. 2.12 or Fig. 2.18 and
als in all. We shall now see how the minimal basis set of eight valence
the Periodic Table as shell atomic orbitals
the increasing effective nuclear charge attracts the electrons more
zing the constraints of the Pauli principle.
(four from each atom, one s and three p) is used to construct strongly. Theeight molecular
result orbitals. Then
is that the molecular s the corresponding homonuclear
orbital energies for p
we shall use the Pauli principle to predict the ground-state electron configurations of the
e the building-up principle in conjunction with the molecular orbital energy level
molecules.
m in the same way as for atoms. The order of occupation of the orbitals is the order
The energies of the atomicFIGURE orbitals
5.7 Energythat
Levelsform
of the basissu*set
12p2are shown on either side of
easing energy as depicted in Fig. 2.12 or the Fig.molecular
2.18. Eachorbital
orbitaldiagram
canHomonuclear
the accommodate
in Fig.Diatomics
2.12. ofWe form # orbitals by allowing overlap be-
p p

Energy level of the homonuclear

two electrons. If more than one orbital is
n to have identical energies, as in the case(as
available
tween atomicfor
ofremarked
occupation
orbitals
pairs of !earlier)
that
orbitals),
(because
the Second
have Period. they
cylindrical
then the orbitals
symmetry around the internuclear axis, which Fig. 2.13 A # orbital can be formed in
is conventionally labelled z. The notation # signifies that the orbital several ways, including s,s overlap, s,p
diatomic molecules of the
cupied separately. In that case, the electrons hasincylindrical
the half-filled orbitals
symmetry; adoptorbitals
atomic
12p2
parallelthat can form p#g*orbitals include the 2s and 2pz overlap, and p,p overlap, with the p orbitals
su*12p2
↑↑), just as is required by Hund’s rule fororbitals atoms on(Section 1.7a). With very few ex-
the two atoms (Fig. 2.13). From these four orbitals (the 2s and the 2pz orbitals directed along the internuclear axis.
second configuration
ns, these rules lead to the actual ground-state period of the Period 2 diatomic
ules. For example, the electron configuration of N2, with 10 valence electrons, is
pg* 12p2
1"2g 1"u2 1!u4 2"2g sg 12p2
Fig. 2.19 The formation of # orbitals
ular orbital configurations are written like those for atoms: the orbitals are listed in by d-orbitalpoverlap.
u 12p2 The orbital has two
of increasing energy, and the number of electrons in each one is indicated by a super- mutually perpendicular nodal planes that
Note that !4 is shorthand for the occupation of two different ! orbitals. intersect along the internuclear axis.
su*12s2

pu12p2
MPL E 2 . 4 Predicting the electron configurations of diatomic molecules sg12s2
sg 12p2
t the ground-state electron configurations of the oxygen molecule, O2, the superoxide ion, O2$, and
roxide ion, O22$.
er We need to determine the number of valence electrons and then populate the molecular orbitals
hem in accord with the building-up principle. An O2 molecule has 12 valence electrons. The first ten
ons recreate the N2 configuration except for the reversal of the order of the 1!u and 2"g orbitals (see
17). Next in line for occupation are the doubly degenerate 1!g orbitals. The last two electrons enter
orbitals separately and have parallel spins. The configuration is therefore su*12s2

" 1" 2" 1! 1!

2
g
2
u
2
g
4
u
2
g
sg12s2
Li2 Be2 B2 C2 N2 O2 F2 Ne2
Bond order 1 0 1 2 3 2 1 0
Unpaired e- 0 0 2 0 0 2 0 0

18

9
electrons, and the bond order is therefore zero. The Ne2 molecule is a transient species, if
it exists at all.
One triumph of molecular orbital theory is its prediction of two unpaired electrons
for O2 . Oxygen had long been known to be paramagnetic, but early explanations for this
phenomenon were unsatisfactory. For example, a special “three-electron bond”5 was
proposed. The molecular orbital description directly explains why two unpaired electrons
1/28/21
are required. In other cases, experimental observations (paramagnetic B2, diamagnetic
C2) require a shift of orbital energies, raising sg above pu, but they do not require major
modifications of the model.

Bond Lengths in Homonuclear Diatomic Molecules

Figure 5.8 shows the variation of bond distance with the number of valence electrons in
second-period p-block homonuclear diatomic molecules having 6 to 14 valence electrons.
Beginning at the left, as the number of electrons increases the number in bonding orbitals
also increases; the bond strength becomes greater, and the bond length becomes shorter.
Bond distance in diatomic species
130 Chapter 5 | Molecular Orbitals
B2 FIGURE 5.8 Bond Distances
160 FIGURE 5.9 Covalent Radii of 82 of Homonuclear Diatomic
Second-Period Atoms. B Molecules and Ions.
150 O22-
F2
Bond distance (pm)

Covalent Radius (pm)

140 78
C2
C
130 O2-

C22- N
120 O2 74
N2+
O
O2+
110
N2 F

100 70
6 7 8 9 10 11 12 13 14 3 4 5.3 Heteronuclear
5 Diatomic 6Molecules | 137
7
Valence electrons Valence electrons
and 2py orbitals of carbon. The distribution of electron density in the 3s and 1p* orbitals
is vital to understand how CO binds to transition metals, a topic to be discussed further in
this section. When the electrons are filled in, as in Figure 5.13, the valence orbitals form
four bonding pairs and one antibondingThis continues
pair up toorder
for a net bond 10 valence
of 3.* electrons in N2, where the trend reverses, because the
+ + - 2-
additional electrons occupy antibonding orbitals. The ions N2 , O2 , O2 , and O2 are
EXAMPLE 5.3 also shown in the figure and follow a similar trend.
19 The minimum in Figure 5.8 occurs even though the radii of the free atoms decrease
Molecular orbitals for HF can be found by using the approach used for CO. The
steadily from B to F. Figure 5.9 shows the change in covalent radius for these atoms (defined
2s orbital of the fluorine atom is more than 26 eV lower than that of the hydrogen
1s, so there is very little interactionfor singlethese
between bonds), decreasing
orbitals. as 2p
The fluorine theorbital
z
number of valence electrons increases, primarily
(-18.65 eV) and the hydrogen 1s (-13.61 eV), on the other hand, have similarpulls
because the increasing nuclear charge ener-the electrons closer to the nucleus. For the
gies, allowing them to combine intoelements boron
bonding and through nitrogen,
antibonding s* orbitals.the
Thetrends shown in Figures 5.8 and 5.9 are similar: as
fluorine
2px and 2py orbitals remain nonbonding,the covalent
each withradius
a pair of electrons.
the atomOverall,
decreases,therethe bond distance of the matching diatomic
molecule
is one bonding pair and three lone pairs; also the
however, decreases.
lone pairsHowever, beyond nitrogen
are not equivalent, in these trends diverge. Even though the
contrast to the Lewis dot approach.covalent
The occupied
radiimolecular
of the freeorbitals
atomsof HF predicttoa decrease (N 7 O 7 F), the bond distances
continue
polar bond since all of these orbitals inare biased toward molecules
the fluorine increase
atom. The(N electron
2 6 O2 6 F2) with the increasing population of
HETERONUCLEAR DIATOMIC MOLECULES
density in HF is collectively distributed
their diatomic
with more
antibonding on the fluorine
orbitals. atomthe
In general relative
bond to the is the more important factor, overriding the
order
hydrogen atom, and fluorine is unsurprisingly the negative end of the molecule.
covalent radii of the component atoms. Bond lengths of homonuclear and heteronuclear
diatomic species are given in Table 5.1.

5.2.4 Photoelectron Spectroscopy

In addition to data on bond distances and energies, specific information about the energies
of electrons in orbitals can be determined from photoelectron spectroscopy.6 In this tech-
nique, ultraviolet (UV) light or X-rays eject electrons from molecules:
O2 + hn(photons) S O2 + + e -
The kinetic energy of the expelled electrons can be measured; the difference between the
energy of the incident photons and this kinetic energy equals the ionization energy (bind-
ing energy) of the electron:
Ionization energy = hv(energy of photons) - kinetic energy of the expelled electron
UV light removes outer electrons; X-rays are more energetic and can remove inner
electrons. Figures 5.10 and 5.11 show photoelectron spectra for N2 and O2, respectively, and
the relative energies of the highest occupied orbitals of the ions. The lower energy peaks (at the
top in the figure) are for the higher energy orbitals (less energy required to remove electrons).
If the energy levels of the ionized molecule are assumed to be essentially the same as those of
EXERCISE 5.3 Use a similar approach to the discussion of HF to explain the bonding in
the hydroxide ion OH - . (Exercise 5.3 by Kaitlin Hellie. Reprinted by permission.)
20
The molecular orbitals that are typically of greatest interest for reactions are the highest
occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO),
collectively known as frontier orbitals because they lie at the occupied–unoccupied frontier.
The MO diagram of CO helps explain its reaction chemistry with transition metals, which
is different than that predicted by electronegativity considerations that would suggest more
electron density on the oxygen. On the sole basis of the carbon–oxygen electronegativity 10

*The classification of the filled s orbitals as “bonding” and “antibonding” in CO is not as straightforward as in, for
example, H2, since the 2s and 2s* orbitals are only changed modestly in energy relative to the 2s orbitals of oxygen
and carbon, respectively. However, these orbital classifications are consistent with a threefold bond order for CO.
 5.3.2 Ionic Compounds and Molecular orbital theory 49
Orbitals
Molecular
Ionic compounds can be considered the limiting form of polarity in heteronuclear
diatomic molecules. As mentioned previously, as the atoms forming bonds differ more in
rogen fluoride electronegativity, the energy gap between the interacting atomic orbitals also increases, and
3σ the
the concentration of electron density is increasingly biased toward more electronegative
Mainly H 1/28/21
nts: In hydrogen fluoride the bonding orbital is more concentrated on the F atom and the anti- H1s
atom in the bonding molecular orbitals. At the limit, the electron is transferred completely
orbital is more concentrated on the H atom. to the more electronegative atom to form a negative ion, leaving a positive ion with a high-
lustration of these general points, consider a simple heteronuclear energy vacantdiatomic
orbital. When two elements with a large difference in their electronegativi-
molecule,
ties (such as Li and F) combine, the result is an ionic bond. However, in molecular orbital
e five valence orbitals available for molecular orbital formation are the 1s orbital of

Energy
terms, we can treat an ion pair like we do a covalent compound. In Figure 5.14, the atomic
the 2s and 2p orbitals of F; there are 1 ! 7 " 8 valence electrons to accommodate in
orbitals and an approximate indication of molecular orbitals for such a diatomic molecule,
molecular orbitals that can be constructed from the five basis orbitals.
LiF, are given. On formation of the diatomic molecule LiF, 1π the electron
F2pfrom the Li 2s
# orbitals of HF can be constructed by allowing an H1s orbital to overlap the F2s
pz orbitals (z being the internuclear axis). These three atomic orbitals combine to 2σ
ree # molecular orbitals of the form ! " c1"H1s ! c2"F2s ! c3"F2p. This procedure Mainly F 1σ F2s
FIGURE 5.14 Approximate LiF
the F2px and F2py orbitalsMolecular unaffected as they have $ symmetry and there is no
Orbitals. (Approximate
H orbital of that symmetry. These $
LiF Molecular orbitals
Orbitals are therefore examples of the non-
by Kaitlin
g orbitals mentioned earlier,Hellie. andReprinted
are molecular
by permission.)orbitals confined to a single atom.
hat, because there is no centre of inversion in a heteronuclear diatomic molecule, we Fig. 2.21 The molecular orbital energy
use the g,u classification for its molecular orbitals. level diagram for HF. The relative positions
re 2.21 shows the resulting energy level diagram. The 1# bonding orbital is predomi- of the atomic orbitals reflect the ionization
F2s in character as the energy difference between it and
Molecular orbital theory
erefore, confined mainly to the F atom and essentially nonbonding. The 2# orbital is
the
49
H1s orbital is large. energies of the atoms.

onding than the 1# orbital and has both H1s and F2p character. The 3# orbital
onding, and principally H1s in character: the 1s orbital has a relatively high energy
red with the fluorine orbitals) and hence contributes3σpredominantly to the high-
Mainly H 4σ
antibonding
centrated on the molecular
F atom andorbital.
the anti- H1s
of the eight valence electrons enter the 2# orbital, forming a bond between the two C2p
2π
Six more enter the 1# and 1$ orbitals; these two orbitals are largely nonbonding
heteronuclear
nfined mainly todiatomic molecule,
the F atom. This is consistent with the conventional model of three
tal
irs on the fluorine atom.orbital
formation are the 1s All the of electrons are now accommodated, so the configura-
Energy

Energy
ence electrons isto1#
the molecule accommodate
2
2#21$4. Oneinimportant feature to note is that all the electrons
heorbitals
five basis thatorbitals.
are predominantly on the F atom. It follows that we can expect the O2p
3σ
an H1s orbital to overlap the F2s 1π F2p
lecule to be polar, with a partial negative charge on the F atom, which is found 1π
three atomic orbitals combine to
mentally. 2σ C2s
! c2"F2s ! c3"F2p. This procedure Mainly F 1σ F2s 2σ
bon
ave monoxide
$ symmetry 21and there is no
e therefore examples of the non- O2s
nts: The HOMO of a carbon monoxide molecule is an almost nonbonding # orbital largely local- 1σ
rbitals confined to a single atom.
C; the LUMO is an antibonding $ orbital.
eronuclear diatomic molecule, we Fig. 2.21 The molecular orbital energy
. Fig. 2.22 The molecular orbital energy level
olecular orbital energy level diagram forlevel carbon
diagrammonoxide
for HF. Theisrelative
a somewhat
positionsmore com-
diagram for CO.
dheexample
1# bonding thanorbital is predomi-
HF because both atomsof have 2s and
the atomic 2p orbitals
orbitals that
reflect the can participate
ionization
normation
it and the H1s orbital is large.
of # and $ orbitals. The energy energieslevel diagram
of the atoms. is shown in Fig. 2.22. The
ally
-statenonbonding.
configuration Theis2# orbital is
nd 2F2p2 character.
1# 2# 1$43#2
CO MOLECULAR ORBITALS
The 3# orbital
rbital has a relatively high energy
#butes
orbital predominantly
is localized to the high-
mostly on the O atom and essentially nonbonding. The 2# 4σ
4σ 2π
is bonding. The 1$ orbitals constitute the doubly degenerate pair of bonding $
s,forming
with mainly a bond C2pbetween
orbitalthe two
character. The C2p HOMO in CO is 3#, which is predomi-
2π
oC2porbitals
z
are largely
in character, nonbonding
largely nonbonding, and located on the C atom. The LUMO is
h thedegenerate
ubly conventional pairmodel of three $ orbitals, with mainly C2p orbital character
of antibonding
23). This combination
accommodated, of frontier orbitals—a full # orbital largely localized on C
so the configura-
Energy
Energy

air
e toofnote empty $ orbitals—is
is that one reason why metal carbonyls are such a characteris-
all the electrons
3σ
urefollows
It of the d metals:
that we can in d-metal
expect the carbonyls, the HOMO 3σ lone pairO2p orbital of CO par-
1π
es on
in thethe formation
F atom, which of a #isbond
found and the LUMO antibonding 1π $ orbital participates
ormation of $ bonds to the metal atom (Chapter 22). C2s
2σ
ough the difference in electronegativity between C and 2σ O is large, the experimental
f the electric dipole moment of the CO molecule (0.1 D) is small. Moreover, the
O2s 1σ
ostend
e of the dipole
nonbonding is onlargely
# orbital the Clocal-
atom despite that being the less electronegative
1σ
atom.
dd situation stems from the fact that the lone pairs and bonding pairs have a com-
stribution. It is wrong to conclude that, because the bonding electrons are mainly Fig. 2.23 A schematic illustration of the
O atom,isOa is the negative Fig. 2.22asThe molecular
ignoresorbital energy leveleffect of
onoxide somewhat moreend com-of the dipole, this the balancing molecular orbitals of CO, with the size of the
e pair on the C atom. The inference of diagram
polarity for CO. electronegativity is particularly
from atomic orbital indicating the magnitude of
nd 2p orbitals that can participate
ble
agram when antibonding
is shown in Fig.orbitals
2.22. The are occupied. its contribution to the molecular orbital.

22

essentially nonbonding. The 2# 4σ

ly degenerate pair of bonding $ 2π
O in CO is 3#, which is predomi-
ed on the C atom. The LUMO is 11
ith mainly C2p orbital character
l # orbital largely localized on C
Energy

carbonyls are such a characteris-

3σ
MO lone pair orbital of CO par-
1π
 Sb Te I
2 . 9 Making estimates using mean bond enthalpies 141 137 133

eaction enthalpy for the production of SF6(g) from SF4(g) given that the mean bond enthalpies * Values are for single bonds except where
otherwise stated (in parentheses); (a) denotes
SF6 are 158, 343, and 327 kJ mol"1, respectively, at 25$C.
aromatic. 1/28/21
make use of the fact that the enthalpy of a reaction is equal to the difference between the
nd enthalpies for broken bonds and the sum of the enthalpies of the bonds that are formed.
s
g) → SF6(g)
on, 1 mol F"F bonds and 4 mol S"F bonds (in SF4) must be broken, corresponding to an
nge of 158 kJ # (4 % 343 kJ)& #1530 kJ. This enthalpy change is positive because energy
in breaking bonds. Then 6 COVALENT
mol S"F bonds (in SFBOND
6 DISTANCE,
) must be formed, correspondingCOVALENT
to an RADIUS
R
nge of 6 % ("327 kJ) & "1962 kJ. This enthalpy change is negative because energy is
AND VAN DER WAALS RADIUS
n the bonds are formed. The net enthalpy change is therefore
530 kJ " 1962 kJ & "432 kJ A B
The length of a covalent bond (bond distance),
d, The
action is strongly exothermic. is the internuclear
experimental value for theseparation and
reaction is "434 mayis inbe
kJ, which
ement with the estimateddetermined
value. experimentally by microwave r A rB
spectroscopy
Estimate the enthalpy of formation of H2S from Sor
8
(adiffraction
cyclic molecule) methods.
and H2. 18 Covalent radius
For an atom X, the value of the single bond
covalent radius, rcov, is half of the internuclear
ronegativity andseparation bond enthalpy in a homonuclear X-X single bond.
The van der
he Pauling scale of electronegativity Waals
is useful radius, rbond
for estimating v, ofenthalpies
an atom andXfor
is half A B
polarities of bonds. of the distance of closest approach of two non-
bonded atoms of X.
of electronegativity was introduced in Section 1.9d, where it was defined as rA rB
an atom of the element to attract electrons to itself when it is part of a com-
greater the difference in electronegativity between two elements A and B, the 19 van der Waals radius
onic character of the A"B bond.
ling’s original formulation of electronegativity drew on concepts relating to
23
s of bond formation. For example, in the formation of AB from the diatomic
olecules,
(g) → 2 AB(g)
hat the excess energy, ∆E, of the A"B bond over the average energy of A"A
nds can be attributed to the presence of ionic contributions to the covalent
defined the difference in electronegativity as
ELECTRONEGATIVITY VALUE
(B)| & 0.102(∆E/kJ mol"1)1/2
P (2.13a)

The disposition of electron density in the region between the two nuclei
of a heteronuclear diatomic molecule X-Y
"B) " 12{B(A"A) # B(B"B)} may be asymmetrical. If the
(2.13b)
effective nuclear charge of Y is greater than that of X, the pair of
electrons in the X-Y covalent bond will be drawn towards Y and away
from X.
Pauling electronegativity values, χp
Electronegativity, χp, was defined by Pauling as ‘the power of an atom in
a molecule to attract electrons to itself ’.
Dχ =χ(A) – χ(B) = (DD)1/2
DD = DA-B(exp) – ½ (DA-A + DB-B)
D = energi disosiasi ikatan dalam eV. χ(H) = 2,2
1 kJ = 6,24×1021 eV atau 1,0 eV = 96,5 kJ/mol

24

12
 values along a series of elements are comparable. This is illustrated
with scaled values of !P (Pauling; red), !M (Mulliken; green) and Since, how
!AR (Allred–Rochow; blue) for first row elements from the p-block. covalent ra
Allred–Roc
1/28/21
the Pauling

!P , !P (H) has been taken as 2.2. Although eq. 2.12 implies Electroneg
1
that the units of !P are eV2 , it is not customary to give units
Despite the
to electronegativity values. By virtue of their different defi-
methods de
nitions, values of ! on different electronegativity scales (see
obtained by
below) possess different units.
EXERCICE In Table 2.2, more than one value of !P is listed for some
exemplifies
in inorgani
elements. This follows from the fact that the electron with-
which, bein
Given that D(H–H) anddrawing
D(F–F) power
in H2 and F2element
of an are 436varies
and 158
withkJ/mol, and state
its oxidation
the experimental value(see
of D(H-F) is 570 kJ/mol. Calculate the can reasona
Section 8.1); remember that the Pauling definition of !P
electronegativity value of F, χ(F). if the elect
refers to an atom in a compound. Electronegativity values
been derive
also vary with bond order. Thus for C, !P has the values
HX, HY,
of 2.5 for a C!C bond, 2.75 for a C¼C bond and 3.3 for
dissociation
a C#C bond. For most purposes, the value of !P ðCÞ ¼ 2:6
of reliability
suffices, although the variation underlines the fact that
such values must be used with caution.
Following from the original concept of electronegativity,
Worked
various scales based upon different ground rules have been
dissociat
devised. We focus on two of the more commonly used
scales, those of Mulliken and of Allred and Rochow; ! Using the f
values from these scales are not directly comparable with D(F!F)=1
25
Pauling values, although trends in the values should be simi- !P (F)=4:0
lar (Fig. 2.11). Scales may be adjusted so as to be compar-
able with the Pauling scale. First, use
pffiffiffiffiffiffiffiffi
Electronegativity values 45 !D ¼ !P ð
OTHER ELECTRONEGATIVITY VALUES
Mulliken electronegativity values, !M
!D ¼ 1:02
In Allred–Rochow
one of the simplest electronegativity
approaches tovalues, !AR
electronegativity,
Mulliken electronegativity value, M the value of !M for an atom to be the mean
andχ Rochow chose as a measure of electronegativity of
Mulliken took This gives t
Allred
of the values theof the first ionization energy, IE1effective
, and the
Mulliken took the value ofanχMatomfor an atom to be the
electrostatic mean
force of the
exerted byvalues
the of
firstnuclear
the first ionization energy, electron
IE1, and Z EA
affinity,
the first
charge 1 (eq. 2.13).
electron
(estimated
eff from EA
affinity, Slater’s
1 rules, see 1:0 eV ( 96
Box 1.5) on the valence electrons. The latter are assumed
IE1 þatEA !D is defin
! ¼reside
M to a distance
1 from the
where IE1nucleus
and EA equal to the covalent
1 are in eV
2
radius, rcov , of the atom. Equation 2.14 gives the method of
ð2:13Þ !D ¼ ½DðB
Allred-Rochow electronegativity value,
calculating valuesχARof the Allred–Rochow electronegativity,
AR
! .
! "
AR Zeff
! ¼ 3590 ' 2 þ 0:744 where rcov is in pm
hough electronegativity values for a given element rcov
scales cannot be expected to be the same, trends in ð2:14Þ
series of elements are comparable. This is illustrated
lues of !P (Pauling; red), !M (Mulliken; green) and Since, however, Slater’s rules are partly empirical and
26 first row elements from the p-block.
Rochow; blue) for covalent radii are unavailable for some elements, the
Allred–Rochow scale is no more rigid or complete than
the Pauling one.

as been taken as 2.2. Although eq. 2.12 implies Electronegativity: final remarks 13
1
s of !P are eV2 , it is not customary to give units
Despite the somewhat dubious scientific basis of the three
gativity values. By virtue of their different defi-
methods described above, the trends in electronegativities
es of ! on different electronegativity scales (see
obtained by them are roughly in agreement, as Fig. 2.11
 518 (a)
N 388 305 (1) 163 (1)
613 (2) 409 (2)
1/28/21
890 (3) 946 (3)
O 463 360 (1) 157 146 (1)
743 (2) 497 (2)
F 565 484 270 185 155
Cl 431 338 200 203 254 242

COMPARISON OF THE ELECTRONEGATIVITY

Br 366 276 219 1
VALUES I 299 238 210 E1
S 338 259 464 523 343 250 2
P 322 (1) Allred–Rochow electroneg
Allred and Rochow chose as a m
Si 318 466 the electrostatic for
an atom
nuclear charge Zeff (estimate
* Values are for single bonds except where otherwise stated (in parenthese
Box 1.5) on the valence elect
to reside at a distance from the
radius, rcov , of the atom. Equat
calculating values of the Allre
with B(A!B) the mean A!B !AR . bond enthalpy. Thus,
cantly greater than the average of !
the nonpolar "
A!A
that there is a substantial ionic contributionZ to the w
!AR ¼ 3590 ' 2eff þ 0:744
enceforina given
Fig. 2.11 Although electronegativity values electronegativity
element between the twocovatoms. Pau
r
from different scales cannot be expectedincreasing oxidation
to be the same, trends in number of the element and the
27 common oxidation
values along a series of elements are comparable. This is illustratedstate.
with scaled values of !P (Pauling; red), !M (Mulliken; green) and Since, however, Slater’s rule
Pauling electronegativities
!AR (Allred–Rochow; blue) for first row elements from the p-block.
are useful
covalent radii for
are estimating
unavailab
ments of different electronegativity
Allred–Rochow and scale
to makeis noqum
of bonds. Binary compounds in which
the Pauling one. the difference
elements is greater than about 1.7 can generally be re
However, this crude distinction was refined by Anto
THE KATELAAR !P , !P (H) has beenTRIANGLE
P
taken as 2.2. Although eq. 2.12 implies
1
Electronegativity: final re
1940s, when they drew a triangle with vertices repr
that the units of ! are eV , it is not customary to give units
2
bonding. The Ketelaar triangle Despite(more appropriately,
the somewhat dubious
to electronegativity values. By virtue of their different defi-
been elaborated by Gordon Sproul,
methods who constructed
described above, the
CsFof ! on different electronegativity scales (see
nitions, values
3 electronegativities (∆!) of the elements in a binary
obtained by them are roughlyc
below) possess different units. A Ketelaar triangle, showing how a plot of
egativity
P ) (Fig.
(!meanfor 2.38). The Ketelaar triangle is
exemplifies. The most useful
MgO2.2, more than one value
In Table averageof !electronegativity
is listed someagainst
elements. This follows from the we shall see how
fact that the electron with- basic
this in concept
inorganiccan be used is
chemistry to cp
2 electronegativity difference can which,
be usedbeing
to based empirical
Ionic
drawing power of an element varies different
with kinds. state
classify theits
bondoxidation
type for binarycan compounds.
Δ

Ionic bonding reasonably be used to pred

(see Section 8.1); remember that the Pauling definition is
of characterized
!P by a large differenc
1 refers to an atom in a compound. difference indicates
Electronegativity that the electronegativity of of
values
if the electronegativities onetw
been derived frombethe single
also varySiO with
2
bond order. Thus for is low,
C, !the
P average
has electronegativity
the values must intermed
Metallic Covalent instance, with ∆! 3.19 HX,
3.3"for and !HY, "X2 , Y2 and H2 ,
2.38, lies at the
Csof 2.5 for a C!C bond, F2 2.75 for a C¼C bond and mean
dissociation enthalpy of the bo
0 a C#C bond. For most purposes, the bonding
value ofis!characterized
P
ðCÞ ¼ 2:6 by a small difference in ele
1 2 3 4 of reliability.
at the base
suffices, although the variation underlines the fact that of the triangle. Binary compounds that a
mean
such values must be used with caution. are typically formed between nonmetals, which comm
Fig. 2.38 A Ketelaar triangle,
Following fromshowing follows
how concept
the original that the covalent region of the triangle is the
of electronegativity,
Worked example 2.4 Es
a plot of average electronegativity
various upon differentofground
scales based against the triangle
rules haveis occupied
been by
dissociation has ∆! " fro
F2, which enthalpy 0a
28
electronegativity difference can be used to
devised. We focus on two of of
the any
more Pauling
commonly electronegativity).
used Metallic bonding
classify the bond typethose
scales, for binary compounds.
of Mulliken and of tronegativity
Allred and Rochow; difference,
! and also
Using thelies towardsdata,
following the esti
bas
values from these scales are not directly comparable with D(F!F)=158 kJ mol!1 D
Pauling values, although trends in the values should be simi- !P (F)=4:0 14 !
lar (Fig. 2.11). Scales may be adjusted so as to be compar-
able with the Pauling scale. First, use the values of !P to
pffiffiffiffiffiffiffiffi
!D ¼ !P P
 Key points: Resonance between Lewis structures lowers the calculated energy of the molecule and
distributes the bonding character of electrons over the molecule; Lewis structures with similar energies –
provide the greatest resonance stabilization. F

A single Lewis structure is often an inadequate description of the molecule. The Lewis
structure of O3 (4), for instance, suggests incorrectly that one O!O bond is different from B 1/28/21
the other, whereas in fact they have identical lengths (128 pm) intermediate between those
of typical single O!O and double O$O bonds (148 pm and 121 pm, respectively). This
deficiency of the Lewis description is overcome by introducing the concept of resonance,

Table 2.1 Lewis structures of some simple molecules* 2 BF4−

66 Chapter 3 | Simple Bonding Theory
H H N N C O
OXIDATION STATES
O S N
– P 3.3 M
O O O O O O When at
Oxidation states can be regarded as the charge that an atom would have F polar bo
if the more electronegative
H
atom
O in a bond acquired the two electrons of more ele
the bond completely.
N S 3 PF3 the bond
H H O O
Determaine the oxidation number of P, S and Cl in the following ion. This pola
molecula
3– 2– O –
O O Exp
O
O P O O S O O Cl O O O dielectric
O O O 4 O3 to be me
Orientati
* Only representative resonance structures are given. Shapes are indicated only for
diatomic and triatomic molecules. field and
What is the oxidation number of S atom in the S2O32- ion? allow ca
the dista
between
Dipo
29
molecule
dipole m
from bon
methane
d- of 1.3 *
calculati
N
MOLECULAR POLARITY H H bond mo
d+
H The
When atoms with different electronegativities are bonded, Net dipole, 1.47 D effect of
the resulting molecule has polar bonds, point in
dipole m
These give the molecules a dipole moment, defined as µ d-
that rein
= Q . r, where r is the distance between the centers of O
positive and negative charge and Q is the difference result of
H H d+
between these charges. sum of th
Net dipole, 1.85 D is the po
Dipole moments of diatomic molecules can be calculated polaritie
directly. In more complex molecules, vector addition of the
(1.63 D),
individual bond dipole moments gives the net molecular d+
dipole moment. sulfur at
N
F F Mol
F d- other pol
Net dipole, 0.23 D with the
FIGURE 3.24 Bond Dipoles melting
30 and Molecular Dipoles. discussio

TABLE 3.
Molecu
15CH Cl
3
CH2Cl
CHCl3
Source: Ex