Molecular symmetry

In this chapter we sharpen the concept of shape into a precise denition of symmetry,
and show that symmetry may be discussed systematically. We see how to classify any
molecule according to its symmetry and how to use this classication to discuss molecular
properties. After describing the symmetry properties of molecules themselves, we turn to
a consideration of the effect of symmetry transformations on orbitals and see that their
transformation properties can be used to set up a labelling scheme. These symmetry labels
are used to identify integrals that necessarily vanish. One important integral is the overlap
integral between two orbitals. By knowing which atomic orbitals may have nonzero overlap,
we can decide which ones can contribute to molecular orbitals. We also see how to select
linear combinations of atomic orbitals that match the symmetry of the nuclear framework.
Finally, by considering the symmetry properties of integrals, we see that it is possible to
derive the selection rules that govern spectroscopic transitions.

11
The symmetry elements of
objects
11.1 Operations and symmetry

elements
11.2 The symmetry classication of

molecules
11.3 Some immediate

consequences of symmetry
Applications to molecular
orbital theory and spectroscopy
11.4 Character tables and

The systematic discussion of symmetry is called group theory. Much of group theory
is a summary of common sense about the symmetries of objects. However, because
group theory is systematic, its rules can be applied in a straightforward, mechanical
way. In most cases the theory gives a simple, direct method for arriving at useful conclusions with the minimum of calculation, and this is the aspect we stress here. In
some cases, though, it leads to unexpected results.

symmetry labels
11.5 Vanishing integrals and orbital

overlap
11.6 Vanishing integrals and

selection rules
Checklist of key equations
Discussion questions

The symmetry elements of objects

Some objects are more symmetrical than others. A sphere is more symmetrical than
a cube because it looks the same after it has been rotated through any angle about any
diameter. A cube looks the same only if it is rotated through certain angles about
specic axes, such as 90, 180, or 270 about an axis passing through the centres of
any of its opposite faces (Fig. 11.1), or by 120 or 240 about an axis passing through
any of its opposite corners. Similarly, an NH3 molecule is more symmetrical than an
H2O molecule because NH3 looks the same after rotations of 120 or 240 about the
axis shown in Fig. 11.2, whereas H2O looks the same only after a rotation of 180.
An action that leaves an object looking the same after it has been carried out is
called a symmetry operation. Typical symmetry operations include rotations, reections, and inversions. There is a corresponding symmetry element for each symmetry
operation, which is the point, line, or plane with respect to which the symmetry operation is performed. For instance, a rotation (a symmetry operation) is carried out
around an axis (the corresponding symmetry element). We shall see that we can
classify molecules by identifying all their symmetry elements, and grouping together

Exercises
Problems

418

11 MOLECULAR SYMMETRY
C2
C3

molecules that possess the same set of symmetry elements. This procedure, for
example, puts the trigonal pyramidal species NH3 and SO 2
3 into one group and the
angular species H2O and SO2 into another group.

C4

11.1 Operations and symmetry elements

Key points (a) Group theory is concerned with symmetry operations and the symmetry elements
with which they are associated; point groups are composed of symmetry operations that preserve
a single point. (b) A set of operations form a group if they satisfy certain criteria.
Fig. 11.1 Some of the symmetry elements
of a cube. The twofold, threefold, and
fourfold axes are labelled with the
conventional symbols.

C3

(a)

C2

(b)
Fig. 11.2 (a) An NH3 molecule has a
threefold (C3) axis and (b) an H2O
molecule has a twofold (C2) axis. Both have
other symmetry elements too.

The classication of objects according to symmetry elements corresponding to operations that leave at least one common point unchanged gives rise to the point groups.
There are ve kinds of symmetry operation (and ve kinds of symmetry element) of
this kind. When we consider crystals (Chapter 19), we shall meet symmetries arising
from translation through space. These more extensive groups are called space groups.
(a) Notation

The identity, E, consists of doing nothing; the corresponding symmetry element is the
entire object. Because every molecule is indistinguishable from itself if nothing is done
to it, every object possesses at least the identity element. One reason for including the
identity is that some molecules have only this symmetry element (1); another reason
is technical and connected with the detailed formulation of group theory.
An n-fold rotation (the operation) about an n-fold axis of symmetry, Cn (the corresponding element) is a rotation through 360/n. The operation C1 is a rotation
through 360, and is equivalent to the identity operation E. An H2O molecule has one
twofold axis, C2. There is only one twofold rotation associated with a C2 axis because
clockwise and counterclockwise 180 rotations have an identical outcome. An NH3
molecule has one threefold axis, C3, with which is associated two symmetry operations, one being 120 rotation in a clockwise sense and the other 120 rotation in a
counterclockwise sense. A pentagon has a C5 axis, with two (clockwise and counterclockwise) rotations through 72 associated with it. It also has an axis denoted C 52, corresponding to two successive C5 rotations; there are two such operations, one through
144 in a clockwise sense and the other through 144 in a counterclockwise sense. A
cube has three C4 axes, four C3 axes, and six C2 axes. However, even this high symmetry is exceeded by a sphere, which possesses an innite number of symmetry axes
(along any diameter) of all possible integral values of n. If a molecule possesses several
rotation axes, then the one (or more) with the greatest value of n is called the principal
axis. The principal axis of a benzene molecule is the sixfold axis perpendicular to the
hexagonal ring (2).
A reection (the operation) in a mirror plane, (the element), may contain the
principal axis of a molecule or be perpendicular to it. If the plane is parallel to the
principal axis, it is called vertical and denoted v. An H2O molecule has two vertical

F
C6

Cl
Br
1 CBrClFI

2 Benzene, C6H6

11.1 OPERATIONS AND SYMMETRY ELEMENTS

Centre of
inversion, i

An H2O molecule has two mirror

planes. They are both vertical (i.e. contain
the principal axis), so are denoted v and v .

Fig. 11.3

419

Fig. 11.4 Dihedral mirror planes (d) bisect

the C2 axes perpendicular to the principal
axis.

Fig. 11.5 A regular octahedron has a centre

of inversion (i).

planes of symmetry (Fig. 11.3) and an NH3 molecule has three. A vertical mirror plane
that bisects the angle between two C2 axes is called a dihedral plane and is denoted d
(Fig. 11.4). When the plane of symmetry is perpendicular to the principal axis it is
called horizontal and denoted h. A C6 H6 molecule has a C6 principal axis and a
horizontal mirror plane (as well as several other symmetry elements).
In an inversion (the operation) through a centre of symmetry, i (the element), we
imagine taking each point in a molecule, moving it to the centre of the molecule, and
then moving it out the same distance on the other side; that is, the point (x, y, z) is
taken into the point (x, y, z). Neither an H2O molecule nor an NH3 molecule has
a centre of inversion, but a sphere and a cube do have one. A C6H6 molecule does have
a centre of inversion, as does a regular octahedron (Fig. 11.5); a regular tetrahedron
and a CH4 molecule do not.
An n-fold improper rotation (the operation) about an n-fold axis of improper rotation or an n-fold improper rotation axis, Sn (the symmetry element), is composed of
two successive transformations, neither of which alone is necessarily a symmetry
operation. The rst component is a rotation through 360/n, and the second is a
reection through a plane perpendicular to the axis of that rotation; neither operation
alone needs to be a symmetry operation. A CH4 molecule has three S4 axes (Fig. 11.6).

S4
C4

(a)

(b) The criteria for being a group

S6

In mathematics, a group has a special meaning and is the basis of the name group
theory for the quantitative description of symmetry. A set of operations constitute a
group if they satisfy the following criteria:
The identity operation is a member of the set.

C6

The inverse of each operation is a member of the set.

If R and S are members of the set, then the operation RS is also a member.
These criteria are satised by a large number of objects, but our concern is with symmetry operations, and we conne our remarks to them.
It is quite easy to see that the symmetry operations of a molecule full the criteria
that let them qualify as a group. First, we have seen that every molecule possesses the
identity operation E. To judge whether the inverse of a symmetry operation is always
present we need to note whether for each operation we can nd another operation (or
the same operation) that brings the molecule back to its original state. A reection
applied twice in succession (which we denote ) is one example. A clockwise n-fold
rotation followed by a counterclockwise n-fold rotation (denoted C nC n+) is another

(b)
Fig. 11.6 (a) A CH4 molecule has a fourfold
improper rotation axis (S4): the molecule
is indistinguishable after a 90 rotation
followed by a reection across the horizontal
plane, but neither operation alone is a
symmetry operation. (b) The staggered
form of ethane has an S6 axis composed
of a 60 rotation followed by a reection.

420

11 MOLECULAR SYMMETRY
example. To every symmetry operation of a molecule there corresponds an inverse
and, provided we include both, criterion 2 is satised.
The third criterion is very special, and is called the group property. It states that,
if two symmetry operations are carried out in succession, then the outcome is equivalent to a single symmetry operation. For example, two clockwise threefold rotations
applied in succession, giving an overall rotation of 240, is equivalent to a single
counterclockwise rotation, so we can write C 3+C 3+ = C 3 and in this case two operations
applied in succession are equivalent to a single operation. A twofold rotation through
180 followed by a reection in a horizontal plane is equivalent to an inversion, so we
can write hC2 = i. Once again, we see that successive operations are equivalent to a
single operation, as criterion 3 requires.
All the symmetry operations of molecules satisfy the three criteria for them constituting a group, so we are justied in calling the theory of symmetry group theory
and using the powerful apparatus that mathematicians have assembled.
11.2 The symmetry classication of molecules
Key point Molecules are classied according to the symmetry elements they possess.

To classify molecules according to their symmetries, we list their symmetry elements

and collect together molecules with the same list of elements. This procedure puts
CH4 and CC14, which both possess the same symmetry elements as a regular tetrahedron, into the same group, and H2O into another group.
The name of the group to which a molecule belongs is determined by the symmetry elements it possesses. There are two systems of notation (Table 11.1). The
Schoenies system (in which a name looks like C4v) is more common for the discussion of individual molecules, and the HermannMauguin system, or International
system (in which a name looks like 4mm), is used almost exclusively in the discussion
of crystal symmetry. The identication of a molecules point group according to
the Schoenies system, which we outline below, is simplied by referring to the ow
diagram in Fig. 11.7 and the shapes shown in Fig. 11.8.

Table 11.1 The notation for point groups*

Ci

Cs

C1

C2

C3

C4

C6

C2v

2mm

C3v

3m

C4v

4mm

C6v

6mm

C2h

2m

C3h

C4h

4/m

C6h

6/m

D2

222

D3

32

D4

422

D6

622

D2h

mmm

D3h

2m

D4h

4/mmm

D6h

6/mmm

D2d

2m

D3d

S4

/m

S6

Th

m3

23

Td

3m

432

Oh

m3m

* In the International system (or HermannMauguin system) for point groups, a number n denotes the
presence of an n-fold axis and m denotes a mirror plane. A slash (/) indicates that the mirror plane is
perpendicular to the symmetry axis. It is important to distinguish symmetry elements of the same type but of
different classes, as in 4/mmm, in which there are three classes of mirror plane. A bar over a number indicates
that the element is combined with an inversion. The only groups listed here are the so-called
crystallographic point groups (Section 19.1).

11.2 THE SYMMETRY CLASSIFICATION OF MOLECULES

421

Molecule

Dh

Ih Y

N C
v

i?

C5?

Two or
more
Cn, n > 2?

N
Linear?

N
N

i?

N O
h

Td

Select Cn with the highest n; then,

are there nC2 perpendicular to Cn?

Y
Dnh Y

h?

Cs

N
Dnd Y

nd?

Ci
Y

?
N

N D
n

Cnh

Cn?

i?

N C
1

h?
N

Cnv Y

nv?
Fig. 11.7 A ow diagram for determining
the point group of a molecule. Start at the
top and answer the question posed in each
diamond (Y = yes, N = no).

N
S2n

n=

S2n

N C
n

Cn

Dn

Cnv

Cone

Pyramid

Cnh

Dnh
Dnd

S2n

Plane or bipyramid

Fig. 11.8 A summary of the shapes

corresponding to different point groups.
The group to which a molecule belongs
can often be identied from this diagram
without going through the formal
procedure in Fig. 11.7.

422

11 MOLECULAR SYMMETRY
(a) The groups C1, Ci, and Cs
COOH
OH

H
H

Centre of
inversion
OH

A molecule belongs to the group C1 if it has no element other than the identity, as in
(1). It belongs to Ci if it has the identity and the inversion alone (3), and to Cs if it has
the identity and a mirror plane alone (4).
(b) The groups Cn, Cnv, and Cnh

COOH
3 Meso-tartaric acid,
HOOCCH(OH)CH(OH)COOH

N
4 Quinoline, C9H7N

C2

A molecule belongs to the group Cn if it possesses an n-fold axis. Note that the symbol
Cn is now playing a triple role: as the label of a symmetry element, a symmetry operation, and the name of a group. For example, an H2O2 molecule has the elements E and
C2 (5), so it belongs to the group C2.
If in addition to the identity and a Cn axis a molecule has n vertical mirror planes v,
then it belongs to the group Cnv. An H2O molecule, for example, has the symmetry
elements E, C2, and 2v, so it belongs to the group C2v. An NH3 molecule has the
elements E, C3, and 3v, so it belongs to the group C3v. A heteronuclear diatomic
molecule such as HCl belongs to the group Cv because all rotations around the axis
and reections across the axis are symmetry operations. Other members of the group
Cv include the linear OCS molecule and a cone.
Objects that in addition to the identity and an n-fold principal axis also have a horizontal mirror plane h belong to the groups Cnh. An example is trans-CHCl=CHCl
(6), which has the elements E, C2, and h, so belongs to the group C2h; the molecule
B(OH)3 in the conformation shown in (7) belongs to the group C3h. The presence of
certain symmetry elements may be implied by the presence of others: thus, in C2h the
operations C2 and h jointly imply the presence of a centre of inversion (Fig. 11.9).

Cl

h
C2

C2

h
OH
B

C3

The presence of a twofold axis and

a horizontal mirror plane jointly imply the
presence of a centre of inversion in the
molecule.
Fig. 11.9

H
5 Hydrogen peroxide, H2O2

Cl
6 trans-CHCl=CHCl

7 B(OH)3

(c) The groups Dn, Dnh, and Dnd

F

8 Boron trifluoride, BF3

C2

C2

9 Ethene, CH2=CH2 (D2h)

We see from Fig. 11.7 that a molecule that has an n-fold principal axis and n twofold
axes perpendicular to Cn belongs to the group Dn. A molecule belongs to Dnh if it also
possesses a horizontal mirror plane. The planar trigonal BF3 molecule has the elements E, C3, 3C2, and h (with one C2 axis along each BF bond), so belongs to D3h
(8). The C6H6 molecule has the elements E, C6, 3C2, 3C ,
2 and h together with some
others that these elements imply, so it belongs to D6h. The prime on 3C 2 indicates that
these three twofold axes are different from the other three twofold axes. In benzene,
three of the C2 axes bisect CC bonds and the other three pass through vertices of the
hexagon formed by the carbon framework of the molecule. All homonuclear diatomic
molecules, such as N2, belong to the group Dh because all rotations around the axis
are symmetry operations, as are end-to-end rotation and end-to-end reection; Dh
is also the group of the linear OCO and HCCH molecules and of a uniform cylinder.
Other examples of Dnh molecules are shown in (9), (10), and (11).
A molecule belongs to the group Dnd if in addition to the elements of Dn it possesses
n dihedral mirror planes d. The twisted, 90 allene (12) belongs to D2d, and the staggered conformation of ethane (13) belongs to D3d.

11.2 THE SYMMETRY CLASSIFICATION OF MOLECULES

C3

C2

C2

Cl

Cl

C2

C4

C2

C2

Au

C2

10 Phosphorus pentachloride, PCl5 (D3h)

C2

11 Tetrachloroaurate(III) ion,
[AuCl4], (D4h)

C2

C2
C3,S6

C2, S4

13 Ethane, C2H6 (D3d)

12 Allene, C3H4 (D2d)

A brief illustration

Host molecules, such as the bowl-shaped cryptophans, that encapsulate smaller guest
molecules have become a focus of interest for a wide variety of applications. Hostguest
complexes are an important means of constructing nanoscale devices, selectively separating mixtures of small molecules on the basis of chemical and physical properties,
delivering biologically active molecules to target cells, and providing unique environments
to catalyse reactions. The shape of the host can inuence both the encapsulation of guest
molecules and the potential application of the complex. The anti and syn cryptophan
isomers (14) and (15), for instance, belong to the groups D3 and C3h, respectively.

OMe

O O

OMe
MeO

OMe
MeO

O O

OMe

14

Another brief illustration

Cucurbiturils are pumpkin-shaped water-soluble compounds composed of six, seven,

or eight glycouril (16) units with a hydrophilic exterior and a hydrophobic interior
cavity. With six glycouril units, for example, the host (17) belongs to the group D6h.

O MeO
O O
OMe

OMe

OMe
MeO

OMe

15

HN

NH

HN

NH

O
O

16 Glycouril

N
O

O
O

O
O

17

O O

423

424

11 MOLECULAR SYMMETRY
Ph
Ph
S4

Ph
Ph

18 Tetraphenylmethane, C(C6H5)4 (S4)

19 Buckminsterfullerene, C60 (I)

(a)

(d) The groups Sn

Molecules that have not been classied into one of the groups mentioned so far, but
that possess one Sn axis, belong to the group Sn. An example is tetraphenylmethane,
which belongs to the point group S4 (18). Molecules belonging to Sn with n > 4 are
rare. Note that the group S2 is the same as Ci, so such a molecule will already have been
classied as Ci.
(e) The cubic groups

A number of very important molecules (e.g. CH4 and SF6) possess more than one
principal axis. Most belong to the cubic groups, and in particular to the tetrahedral
groups T, Td, and Th (Fig. 11.10a) or to the octahedral groups O and Oh (Fig. 11.10b).
A few icosahedral (20-faced) molecules belonging to the icosahedral group, I
(Fig. 11.10c), are also known: they include some of the boranes and buckminsterfullerene, C60 (19). The groups Td and Oh are the groups of the regular tetrahedron (for
instance, CH4) and the regular octahedron (for instance, SF6), respectively. If the object
possesses the rotational symmetry of the tetrahedron or the octahedron, but none of
their planes of reection, then it belongs to the simpler groups T or O (Fig. 11.11). The
group Th is based on T but also contains a centre of inversion (Fig. 11.12).

(b)

(c)

Fig. 11.10 (a) Tetrahedral, (b) octahedral, and (c) icosahedral molecules are drawn in a way that shows their relation to a cube: they belong to
the cubic groups Td, Oh, and Ih, respectively.

Fig. 11.11 Shapes corresponding to the

point groups (a) T and (b) O. The presence
of the decorated slabs reduces the
symmetry of the object from Td and Oh,
respectively.

(a)

(b)

11.3 SOME IMMEDIATE CONSEQUENCES OF SYMMETRY

425

Ni
5
Ag

Fig. 11.12 The shape of an object belonging

to the group Th.

SC(CH3)2CH(NH2)CO2
20

A brief illustration

The ion [Ag8Ni6{SC(Me)2CH(NH2)CO2}12Cl]5 (20) is a tetrahedral host belonging to

the group Th.
(f) The full rotation group

The full rotation group, R3 (the 3 refers to rotation in three dimensions), consists of
an innite number of rotation axes with all possible values of n. A sphere and an atom
belong to R3, but no molecule does. Exploring the consequences of R3 is a very
important way of applying symmetry arguments to atoms, and is an alternative
approach to the theory of orbital angular momentum.

Cp = C5H5
Ru

Example 11.1 Identifying a point group of a molecule

Identify the point group to which a ruthenocene molecule (21) belongs.

Method Use the ow diagram in Fig. 11.7.
Answer The path to trace through the ow diagram in Fig. 11.7 is shown by a green

21 Ruthenocene, Ru(Cp)2

line; it ends at Dnh. Because the molecule has a vefold axis, it belongs to the group
D5h. If the rings were staggered, as they are in an excited state of ferrocene that lies
4 kJ mol1 above the ground state (22), the horizontal reection plane would be
absent, but dihedral planes would be present.

Cp = C5H5

Fe

Self-test 11.1 Classify the pentagonal antiprismatic excited state of ferrocene (22).

[D5d]
22 Ferrocene, Fe(Cp)2

11.3 Some immediate consequences of symmetry

Key points (a) Only molecules belonging to the groups Cn, Cnv, and Cs may have a permanent
electric dipole moment. (b) A molecule may be chiral, and therefore optically active, only if it does
not possess an axis of improper rotation, Sn.

Some statements about the properties of a molecule can be made as soon as its point
group has been identied.

426

11 MOLECULAR SYMMETRY
(a) Polarity

(a)

(b)

Fig. 11.13 (a) A molecule with a Cn axis cannot

have a dipole perpendicular to the axis, but
(b) it may have one parallel to the axis. The
arrows represent local contributions to the
overall electric dipole, such as may arise
from bonds between pairs of neighbouring
atoms with different electronegativities.

S2

A polar molecule is one with a permanent electric dipole moment (HCl, O3, and NH3
are examples). If the molecule belongs to the group Cn with n > 1, it cannot possess
a charge distribution with a dipole moment perpendicular to the symmetry axis
because the symmetry of the molecule implies that any dipole that exists in one direction perpendicular to the axis is cancelled by an opposing dipole (Fig. 11.13a). For
example, the perpendicular component of the dipole associated with one OH bond
in H2O is cancelled by an equal but opposite component of the dipole of the second
OH bond, so any dipole that the molecule has must be parallel to the twofold symmetry axis. However, as the group makes no reference to operations relating the two
ends of the molecule, a charge distribution may exist that results in a dipole along the
axis (Fig. 11.13b), and H2O has a dipole moment parallel to its twofold symmetry axis.
The same remarks apply generally to the group Cnv, so molecules belonging to any of
the Cnv groups may be polar. In all the other groups, such as C3h, D, etc., there are symmetry operations that take one end of the molecule into the other. Therefore, as well
as having no dipole perpendicular to the axis, such molecules can have none along the
axis, for otherwise these additional operations would not be symmetry operations.
We can conclude that
Only molecules belonging to the groups Cn, Cnv, and Cs may
have a permanent electric dipole moment.

Criterion for
being polar

For Cn and Cnv, that dipole moment must lie along the symmetry axis. Thus ozone,
O3, which is angular and belongs to the group C2v, may be polar (and is), but carbon
dioxide, CO2, which is linear and belongs to the group Dh, is not.
(b) Chirality
Some symmetry elements are
implied by the other symmetry elements
in a group. Any molecule containing
an inversion also possesses at least an S2
element because i and S2 are equivalent.
Fig. 11.14

A chiral molecule (from the Greek word for hand) is a molecule that cannot be
superimposed on its mirror image. An achiral molecule is a molecule that can be
superimposed on its mirror image. Chiral molecules are optically active in the sense
that they rotate the plane of polarized light. A chiral molecule and its mirror-image
partner constitute an enantiomeric pair of optical isomers and rotate the plane of
polarization in equal but opposite directions.
A molecule may be chiral, and therefore optically active, only
if it does not possess an axis of improper rotation, Sn.

COOH

Criterion for
being chiral

CH3

NH2

23 L-Alanine, NH2CH(CH3)COOH

COOH
H
H

NH2

24 Glycine, NH2CH2COOH

However, we need to be aware that such an axis may be present under a different
name, and be implied by other symmetry elements that are present. For example,
molecules belonging to the groups Cnh possess an Sn axis implicitly because they
possess both Cn and h, which are the two components of an improper rotation axis.
Any molecule containing a centre of inversion, i, also possesses an S2 axis, because i
is equivalent to C2 in conjunction with h, and that combination of elements is S2
(Fig. 11.14). It follows that all molecules with centres of inversion are achiral and
hence optically inactive. Similarly, because S1 = , it follows that any molecule with a
mirror plane is achiral.
A molecule may be chiral if it does not have a centre of inversion or a mirror plane,
which is the case with the amino acid alanine (23), but not with glycine (24).
However, a molecule may be achiral even though it does not have a centre of inversion. For example, the S4 species (25) is achiral and optically inactive: though it lacks
i (that is, S2) it does have an S4 axis.