X How to use tha Programmes

Learning a subjecl (as opposed to just reading a book about it) can be
a longjob. Don't get discouraged ifyou find the programmes taking a
long time. Some students find this subject easy and work througb
each programme in about an hour or even less. Others have been Programme1
known to take up to four hours for sorne programmes. Provided
the programme objectives are achieved the time spent is relatively
unimportant. Symmetry Elements and
After completing each programme try the test at the end and only
proceed to the next programme if your test score is up to the standard
Operations
índicared.

Each programme finishes with a page of revision notes which should

be helpful either to summarise the progranuue before or after use, or
to serve as revision material later. ·
Objectives
I hope you find the programmes enjoyable and .useful.
After completing this programme, you should be able to:
l. Recognise symmetry elements in a molecule .
. 2. List the symmetry operations generated by each element.
3. Combine together two operations to find the equivalent
single operation.
All three objectives are tested at the end of the programme.

Assumed Knowledge

Some knowledge of the shapes of sjmple molecules is assumed.

2 Programme1 Symmetry Elements and Operations 3

Symmetry Elements and Operations 1.3 Rotate by half a turn about an axis through a vertex i.e. turn
it over

GA. A
1.1 The idea of symmetry is a familiar one, we speak of a shape
as being "symmetrical", "unsymmetrical" or even 1 'more
symmetrical than sorne other shape". For scientific purposes,
however, we need to specify ideas of symmetry in a more 3�2 ---------•1�2
quantitative way.
How many operations of this type are possible?
Which of the following shapes would you cal! the more sym­
metrical?
1.4 · Í'hree, one through each vertex.
We have now specified the first of our symmetry operations,
called a PROPER ROTATION, and given the symbol C.
The symbol is given a subscript to indicate the ORDER of
the rota tion. One third of a turn is called C3 , one half a turn
C2 , etc.
What is the symbol for the operation:
A

1.2 If you said A, it shows that our minds are at leas\ working
along similar lines!

We can put the idea of symmetry on a more quantitative 1.5 C4 • It is rotation by ¼ of a turn.
basis. If we rotate a piece of cardboard shaped like A by
one third of a turn, the result looks the same as the starting A symmetry operation is the operation of actually doing
point: something to a shape so that the result is indistinguishable

6 6
1 3
rotate
--""1c "o"'ckw;.c...i �s. -e---+
3 2 2 1
A A
Since A and A' are indistinguishable (not identical) we say
from the initial state. Even if we do not do anything, how­
ever, the shape still possesses an abstrae\ geometrical
property which we term a symmetry element. The element
is a geometrical property which is said to generate the opera­
tion. The element has _the same symbol as the operation.
What obvious symmetry element is possessed by a regular
six-sided shape:

o
that the rotation is a symmetry operation of the shape.

Can you think of another operation you could perform on a

triangle of cardboard which is also a symmetry operation?
(Not the anticlockwise rotation!)
4 Programmeí Symmetry E!ements and Operations 5

1.6 C6 , a six-fold rotation axis, because we can rota te it by½ of a 1.8 We get back to where we started i.e.
turn

601
5
2.

3
506
4 2
1 502
4
1

4 3
One element of symmetry may generate more than one
operation e.g. a C3 axis generales two operations called C3
andel:
3
The shape is now more than indistinguishable, it is
IDENTICAL with the starting point. We say that el, or
indeed any cg = E, where E is the IDENTITY
. '_OPERATION, or the operation of doing nothing. Clearly
this operation can be performed on anything because every-
thing looks the same after doing nothing to it! If this sounds
a bit trivial I apologise, but it is necessary to include the
identity in the description of a molecule's symmetry in
order t9 be able to apply the theory of Groups.

We have now seen two symmetry elements, the identity, E,

What operations are generated by a C5 axis? and a proper rotation axis C 0 • Can you think of a symmetry
element which is possessed by ali planar shapes?
1.7 e,, el, el, e)
1.9 A plane of symmetry.

This is given the symbol a (sigma). The element generales

only one operation, that of reflection in the plane.

Why only one operation? Why can't we do it twice - what is

(;-2?

1.10 a 2 = E, the identity, because reflection in a plane, followed

by reflection back again, returns ali points to the position
from which they started, i.e. to the identica/ position.
What happens if we go one stage further i.e. C)?
Many molecules have one or more planes of symmetry. A flat
molecule will always have aplane in the molecular plane e.g.
H 20, but this molecule also has one other plane.

Can you see where it is?

6 Programmei Symmetry Elements and Operations 7

AT THIS STAGE SOME READERS MAY NEED TO MAKE 1.13 E C2 O" O"' Don't forget E!
USE OF A KIT OF MOLECULAR MODELS OR SOME SORT
OF 3-DIMENSIONAL A!D. IN THE ABSENCE OF A PROPER Each of these elements generates only one operation, so the
KIT, MATCHSTICKS AND PLASTICINE ARE QUITE GOOD, four symbols also describe the four operations.
AND A FEW UNES PENCILLED ON A BLOCK OF WOOD
HAVE BEEN USED.
Pyridine is another flat molecule like water. List its symmetry
elements.
l.!Oa You were trying to find a second
plane of symmetry in the water

1.11
molecule:

cr'
O" is the plane of the molecule,
O"' js at right angles to it and
© N
c.f. H
"o/
H

,.+----,,t--7 cr reflécts one H atom to the 1.14 E C2 O" O"' i.e. the same as water.
other.
Many inolecules have this set of symmetry elements, so it is
convenient to classify them al! under one name, the set of
symmetry operations is called the C2v point group, but more
The water molecule can also be brought to an indistinguish- about this nomenclature later.
able configuration by a simple rotation. Can you see where
the proper rotation axis is, and what its arder is? There is a simple restriction on planes of symmetry which is
rather obvious but can sometimes be helpful in finding
planes. A plane must either pass through an atom, or else
1.12 C2 , a twofold rotation axis, or rotation by half a turn. that type of atom must occur in pairs, symmetrica!ly either
side of the plane. Take the molecule SOCI2 , which has a
cr' plane, and apply this consideration. Where must the plane
be?

1.15 Through the atoros S and O because there is only one of

each:

A C2 axis passing through space is the hardest of al! sym-

metry elements to see. lt will be much easier to visualise if
you use a model of the molecule.
This completes the description of the symmetry of water. It
actually has FOUR elements of symmetry - one of which is The molecule NH 3 possesses planes. Where must they lie?
possessed by ali molecules irrespective of shape. Can you list
al! four symmetry elements of the water molecule?
8 Programme1 Symmetry Elements and Operations 9

1.16 Through the nitrogen (only one N), and through at least one 1.18
hydrogen (because there is an odd number of hydrogens).
Look at a model and convince yourself that this is the case.
A further element of symmetry is the INVERSION CENTRE,
í. This generates the operation of inversion through the centre.
Draw a line from any point to the centre ofthe molecule, and H✓C\_.__ H
produce it an equal distance the other side. If it comes to an
equivalen! point, the operation of inversion is a symmetry
operation. e.g. ethane in the staggered conformation:
CH 4 , C2 H 2, C2 H 4, SO2 Cl 2 fulfil the rules, i.e. have no atoms
present in odd numbers, or have only one such atom.
Which of these actually have inversion centres?
H o
1 1
H-C=:1C-H
CF'J-o
Cl
H

N.B. The operation of

inversion cannot be
physically carried
H

~r:::-H
·I;b~C~
.. H 1.19 Only C2H 2 and C2H4. Both have an inversion centre midway
· between the two carbon atoms.

What is the operation i2?

out on a model.
H/ H 1.20 i2 = E, for the same reason that ,;2 = E (Frame 1.10).
Which of the following have inversion centres We now have the operations E, u, C0 , i. Only one more is
necessary in order to specify molecular symmetry completely.
That is called an IMPROPER ROTATION and is given the
symbol S, again with a subscript showing the order of the
axis. The element is sometimes ca!led a rotation-reflection
B c D E axis, and this describes the operation very well.

The S0 operation is rotation by 1/n of a turn, fo!lowed by

1.17 Only B and D e.g., for C, the operation i would take point x reflection in a plane perpendicular to the axis, e.g. ethane in
to point y which is certainly not equivalen!: x the staggered conformation has an S6 axis because it is
brought to an indistinguishable arrangement by a rotation

An inversion centre may be:

(u
Y
of 1/6 of a turn, followed by reflection:

a. In space in the centre of a molecule (ethane, benzene); or

b. At a single atom in the centre of the molecule (D above). rotatc cla<:kwisc by 116 tum

If it is in space, all atoms must be present in even numbers,

spaced either side of the centre. If it is at an atom, tMn that
type of atom only must be present in an odd number. Hence a
molecule AB 3 cannot have an inversion centre but a molecu]e
AB4 might possibly have one. N.B. Neither C6 nor u are present on their own.
Use this consideration to decide which of the following In this example the effect of the symmetry operation has been
MIGHT POSSIBLY have a centre of inversion. shown by labelling one comer ofthe drawing. Draw the posi-
NH3 CH4 C2H2 C2H4 SOCl2 SO 2Cl 2 tion ofthe label after the S6 operation is applied a second time.
10 Programme1 Symmetry E!ements and Operations 11

1.21 1.24 S¿ = el for the same reason that S¡ = e3 (Frame1.22) i.e.

we have now rotated by 1/6 of a turn 4 times(= ej), and
reflected 4 times (= E)

s¡ is a unique operation, and sz = E. This is again true for

any S0 of even n.

I TI III
Let us now look at S0 of odd n because the case is rather
different from even n. It may at first seem rather a trivial
Now consider what single symmetry operation will take this operation, because the C. axis and a perpendicular plane
molecule from state I direct to state III i.e. what single opera- must both be present, but it is necessary to include it to
tion is the same as S¡? apply Group Theory to symmetry.

Use as the model a flat equilateral triangle with one vertex

1.22 S¡ = e3, rotation by one third o(a turn, because the moje- "labelled"; this !abe! is only to help us to follow the effect of
cule has been rotated by 2/6 of a turn (= e3) and reflectéd the operations, for example the application of S3 moves the
twice (o-2 = E). !abe! as shown:

What happens to the marker if S6 is applied once more, i.e.

what single operation has the samé effect as sl (use a model
Write down the result
or the diagram above).
of applying S3 clockwise
once, twice and then
1.23 S¡ = i. In general s~1' = i if n is even and n/2 is odd. The three times.
operation s~1' is then not counted by convention. If S0 (n
even) is present, and n/2 is odd, i is present but the converse
1.25
is not necessarily true.

Now apply S6 once more, so that it has been applied four

times in al!.

What other operation gives the same result as S¿?

In contras! to S6 and e3 , applying the operation n times,

where n is the order of the axis <loes not bring us back to
the identity.

Keep going, then, when do we get E?

12 Programme1 Symmetry Elements and Operations 13

1.26 l.28 e6 e¡ e¡ et e¡ e~
]s1~~ e3e2el E
Again, by convention, only the operations C6 and e¡ are

~~~ -2_.'C=> counted, the others are taken to be generated by C3 and C 2

axes colinear with C 6.

This result is quite genernl, for n odd S~º = E, because we We have just been looking at the operations generated by
have rotated through two whole circles, and reflected an even a particular symmetry element, let us now turn to the identi-
number of times. fication of symmetry elements in a molecule. Y ou must first
be quite sure you appreciate the difference between a sym-
The equilateral triangle also has E, e3, and CJ among its nietry element and the symmetry operation(s) generated by
elements of symmetry. Many of the operations we have gen- the · element. If you are not confident of this point, have
erated by using the S3 element of symmetry c0uld have been another look at frames 1.5 to l. 13.
generated by using other elements' e.g., Sj = el, Write these
equivalents underneath the symbol Sj ·where appropriate: · · Sorne molecules have a great many symmetry elements, sorne
ofwhich'are not immediately obvious e.g. XeF 4 :
s, sl sl Sj sl sí
e.g. el F "•~·_ _._,__ _ • F
/ ;;)t~ 7 · · · e~
1
also E, i
F ... =::.._...+.;,-'"'"·.. F o-h (molecular plane)
e\ ·•. . e; 2o- vertically through C2
1.27 S3 Sj sl sí e, 2CJ' vertically through Cf
el E s,
By convention, only S3 and Sl are counted as distinct opera-
tions generated by the S3 symmetry element. Hence the complete list of symmetry elements is:

Do a similar analysis for the symmetry element C6 (proper

rotation axis) of benzene, which also has C 3 and C2 axes
colinear with the C 6 . Clearly e¡ = C3 since rotation by two List the symmetry elements of the following molecules:
sixths of a turn is the same as rotation by one third of a turn:
Write the operations which have the same effect as C6 e¡ e¡ Cl
C¡ e¡and cf 1 N (assume CH3
groups
Cl/
B
"'el H
lii\H spherical)

If there is a set of, say, three equivalent planes, write them as

3o-, but ifthere are three non-equivalen! planes, write (fo-' (f".
Similarly for other elements.
14 Programme1 Symmetry Elements and Operations 15

1.29 BCl 3 : E e, s, 3C 2 3,,. (Y (a somewhat similar 1.31 ,,a'

/cr
NH 3 :
Butene:
E
E
e,
e, (Y
3,,. case to XeF4)
H
C2
/
0
-
cr
H
,0
C2
--+
fI /
0
H

We will now ]ook at what happens if two symmetry opera-

/
tions are combined, or performed one after the other. The
result is always the same as doing one symmetry operation
alone, so we can write an equation such as:
"' cr'

In this case the tWo operations COMMUTE i.e., ,,.e, = e,,,.,

but this is not always true .

. Use this diagram with an arrow to set up a complete multi-

This equation means that the operation C2 followed by the plication table for the symmetry OPERATIONS ofthe water
operation ,,. gives the same .result as the operation ,,.', Note mó]ecule, putting the product of the top operation, then the
that the order in which the operations are performed is from side operation, in the spaces:
right to left. I apologise for the introduction of back to .front
methods, but this is the conventiorl universally used in the
E e, (Y
,,.,
mathematics of operators, and the reason for it will become
evident when we begin to use matrices tb represent symmetry E
operations.

Confirm that this relationship is in fact true for the water

molecule. lt ¡µay hélp to put a small label on your model to (Y
show the effect of applying the operations:
,,.,
,,a'
H /O g 1.32 E e, (Y
,,.,
E E e, (Y
,,.,
Draw the position of the arrow after applying C2 , and then e, C2 E
,,., (Y

after applying " to the result. Hence confirm that "C2 = ,,., . ,,.,
(Y (Y E

1.30 ,,, cr' ,,., ,,., (Y e, E

/cr
H
C2
/
/
0
A - C2
H /
0
H
cr
--+
,/
0
H

"' cr' /
What is the effect ofreversing the order ofthe operations? i.e.
what is the product e,,,. (,,.
followed by C2 )?
16 Programme1 Symmetry Elements and Operations 17

You should now be able to: Symmetry Elements and Operations Test
A. Recognise symmetry elements in a molecule.
B. List the operations generated by each element. l. List the symmetry elements of the molecules.
C. Combine together two operations to find the equivalent single
operation. A CH 3 CH 3
l'm afraid the next page is a short test to see how well you have "-._ e C/ (assume CH 3 spherical)
learned about elements and operations. After you have done it, /
mark it yourself, and it will give you sorne indication of how well
you have understood this work.
H
"H

+
B Cl
NH 3
(assume NH 3 spherical)

H3N
Br
e Cl

ea
+

Co ¿}•n
Cl

D HC CH

HC
/ e \CH
~c/
H
18 Programmei Symmetry Elements and Operations 19

2. Set up the multiplication table for the operations of the mole- Answers
cule trans but-2-ene. Apply the top operation then the side
operation: Give yourself one mark for each underlined answer you get right.
(The others are so easy, they are not worth a mark!)
E

"
H CH 3 (J
,
E l. A. f; e, !!: !!:_
/
/C=C"-, ,
CH 3 H
B. E C4 e, 2a 2a
, ,,
e. E e, e, e, i !!: !!:_ !L
,
(J
D. E e, se, !!: .k S.,
Total= 20

2. E e, (J

3. In this question you have to state 'the single symmetry opera-

E E e, (J
tion of XeF4 which has the same effect as applying a given
operation severa! times. The diagram below shows the location
e, e, f; ! !!:
of the symmetry elements concerned.
(J (J
l f; e,

!!: e, f;
Total= 9

3. A. si= e, E. el= el
B. S¡ = S¡ F. ej =E
What operation has the same effect as:
e. S4=f; G. a' =E
A. si E. e¡ D. ei = e, H. E
1·2 =_

B. S¡ F. e! Total= 8
e. s! G. a' Grand Total = 37
D. e~ H. i'
20 Programme1
To be able to proceed confidently to the next programme you should
have obtained at least:
Question 1 (Objective 1) 15/20 (Frames 1.1-1.20)
Question 2 (Objective 2) 7/9 (Frames 1.28-1.32)
Question 3 (Objective 3) 4/8 (Frames 1.6-1.10, 1.19-1.28).
If you have not obtained these seores you would be well
advised to return to the frames shown, although a low
score on question 3 is less serious than the other two.
Symmetry Elements and Operations 21
Symmetry Elements and Operations
Revision Notes
The symmetry of a molecule can be described by listing all the sym-
metry elements of the molecule. A molecule possesses a symmetry
element if the application of the operation generated by the element
]eaves the molecule in an indistinguishab/e state. There are five differ-
ent elements necessary . to complete!y specify the symmetry of ali
possible molecules: ·
E the identity
Cn proper rotation axis of order n
G a plane of symmetry
an inversion centre
Sn improper (or rotation-reflection) axis of order n.
Each of the elements E, G, i only generales one operation, but Cn and
Sn can generate a number of operations because the effect of applying
the operation a number of times can count as separate operations
e.g., the C 3 element generales operations C3 and C~. Some such multi-
ple applications of an operation have the same effect as a single
application of a different operation. In these cases only the single
case is counted, e.g., C¡ = C2 , and only C 2 is counted.
If two operatio ns are performed successively on a molecule, the resu!t
is always the same as the app!ication of only one different operation.
It is therefore possible to set up a multiplication table for the sym-
metry operations of a molecu!e to show how the operations combine
together.
When writing an equation to represent the successive application of
symmetry elements it is necessary to remember that G G 1 C4 meaos C4
followed by G\ followed by G.
 Point Groups 23

Point Groups

2.1 Write down the symbols of the FIVE elements needed to

Programme2 completely specify molecular symmetry.

Point Groups 2.2 E C S o- i

What are the names of these five elements of symmetry?

2.3 E - The identity element

C ~ Proper rotation axis
s· - Improper rotation (or rotation-refiection) axis
o- - Plane of symmetry
Cl Cl
Objectives i - Inversion centre '°'B/
1
List all the symmetry elements of Cl
After completing this programme you should be able to:
l. State the point group to which a molecule belongs.
2.4 E C3 3C2 o- 3o-' S3
2. Confirm that the complete set of symmetry operations of a
molecule constitutes a group. If you have gol these three questions substantially correct
3. Arrange a set of symmetry operations into classes. you may proceed, otherwise return to Programme 1-
The first of these objectives is vital to the use of group theory and is Symmetry Elements and Operations. HC- CH
the only one tested at the end of the programme.
List all the symmetry elements of
"0/
fi
Assumed Knowledge
2.5 E C3 3C2 o- 3o-' S3
A knowledge of simple molecular shapes, and of the contents of i.e. exactly the same as BC1 3
Programme 1 is assumed.
There are many other examples of severa! molecules having
the same set of symmetry elements, e.g. list all the symmetry
elements of
H H
@ 'c=é'-.
/
N HOOC COOH
24 Programme 2 Point Groups 25

2.6 Ali three of these molecules (and many more!) have the 2.8 Four
elements
. F~ /F······/

In the same way all square planar molecules contain the .............................. xe----~
elements E C4 C2 (= C¡) 4C 2 cr 4cr' i S4 , regardless of
the chemical composition of the molecule e.g. F/ ~F
F F e{ ······c2
"/ Xe
etc. Cz
F/ "' F Let us look now ata flat triangular molecule, say BC1 3:

It is convenient to classify all .such molecules by a single X

a flat square molecule is D 4h.

Can you suggest the symbol for a flat

· ©•: ·
symbol which summarises their symmetry. This symbol for
Y..............
Cl Cl.......
........... Y

hexagonal molecule like benzene:

,'B....-
..P z
2.7 D 6h the syrrlmetry is similar to that of the square planar case,
but the principal axis is a 6-fold axis not a 4-fold axis.

The symmetry symbol consists of three parts: What are the symmetry elements labelled X, Y, and Z?

The number indica.tes the order of the principal (i.e. highest

order) axis. This is conventionally taken to be vertical. 2.9 X= C 3 axis
Y= C2 axes
The smal/ letter h indicates a horizontal plane. Z = plane of symmetry
The capital /et ter D indica tes that there are n( = 6 for
benzene) C2 axes at right angles to the principal Cn axis The principal C 3 axis is taken, conventionally to be vertical,
(C 6 for benzene): so the plane is a horizontal plane (crh), and there are three C2
axes at right angles to the principal axis.

What, therefore, is the symmetry symbol of the BC13 mole-

cule? (frame 2.7 may help).
Two-fold axes

How many two-fold axes like this are there in a flat square
molecule like XeF4 ?
26 Programme 2 Point Groups 27

2.10 2.11 D 3ct, a model will help to convince you of the elements of
Cz symmetry in this case, but the following diagram is looking
.... down the principal, vertical, 3-fold axis:
'• ···········••'
CTct ,/P,,
..<Jd
º"i . .________ 3 vertical planes ( <Jd )
,/ ----_::,-.-.} :~'.~-.·,:::~---e,
···•• .... %
c·'.2...-
,' \;,
/
3C2 axes
3-fold principal ax.is

T4is is another case like frame 1.12 in which the C2 axis

3h \,_
Point group sym/bol:D\ .
p·asses through space and not along a bond, These axes are
·ho_rizontal plane quite difficult to see anda molecular model may be necessary.
In the eclipsed conformation ethane has an additional ele-
3C2 axes 3-fold principal ment of symmetry. Can you see from the diagram (or a
(horizontal) axis (vertical) model) what the extra element is?

The molecule is said to belong to the D 3h POINT GROUP.

2,12 A horizontal plane of symmetry, "h
Let us now get a bit more general, and call the principal axis
Cn, so that its order, n, can be any number. What <loes this make the point group of ethane in the
eclipsed conformation?
If there is no horizontal plane of symmetry, but there are n
vertical planes as well as nC 2 axes, the point group is Dnct · '\ H
H-..c_,,/"'
The D and the number mean the same as before but the small
d stands for DIHEDRAL PLANES, because the n vertical 1
planes lie between the nC2 axes. H ___., C --.,______

Ethane in the staggered conformation belongs to a Dnct point H

group. Decide on the value of n. from the following diagram
(looking down the principal axis), and hence state the point
group to which ethane belongs.
J H
2.13 D 3h i.e, in the eclipsed conformation the horizontal plane
takes precedence over the dihedral planes in describing the
symmetry.
Sorne molecules have a principal Cn axis, and nC2 axes at
right angles, but no horizontal or vertical (dihedral) planes.
There is then no need to include h or d in the symmetry
symbol. If the principal axis is a 3-fold axis what is the sym-
metry symbol in this case?
28 Programme 2 Point Groups 29

2.14 Di i.e., it has a 3-fold axis and three C2 axes at right angles, 2.16 C 3h i.e. it has a principal C 3 axis, no horizontal C2 axes, and
hence Di, but no "h or a "ct, so no additional symbol is a horizontal plane
necessary.
An example of an ion of this symmetry is: What is the point group of the flat ion:

(en= NH 2CH 2 CH 2NH 2)

You will probably need a model of the ion to see the axes,
2.17 Dsh i.e. it has a C 5 (vertical), 5 C2 axes at right angles, anda
although an alternative diagram of the structure shows its
horizontal plane.
symmetry very well:
List the four symmetry H COOH
elements of fumaric acid: 'c=c!
(CARE! There is again a
C2 axis through space). HOOC/ "' H

If the principal Cn axis is not accompanied by nC2 axes, the 2.18 E, C2, "h, i. What does this make the point group symbol?
first letter of the point group is C. A horizontal plane is
looked for first, and is shown by a little h. If "h is not present, 2.19 C 2h i.e. it has a C2 axis and a horizontal plane.
n vertical planes are looked for and are shown by a small v.
e.g. O C2 , no C2 at right angles no "h, The molecule H 20 2 and the ion cis[Co(en) 2Cl 2¡+ both have
but 2crv :. point group C2v only the identity and one proper axis of symmetry. They both
/'\
H , H belong to the same point group. Can you say which one it is?
N
d, /~\H (A model, or the diagrams below, might help.)
What is the point group of H

o-o
2.15 C 3v i.e. it has a principal Ci axis and H/
3 vertical planes.
Remember that all flat molecules º"'- /º -- H
I \
H H
havc a plane of symmetry in the B
molecular plane. Try to decide /
the point group of a free boric 0
acid molecule which has no /
vertical planes or horizontal C2 axes. H
30 Programme 2 Poínt Groups 31

2.20 C 2 . They both have a C 2 axis: 2.22 A. Cs

+
B. C1
º~º
¡
H ,¡ '
H
................. e,
There is a simple way of classifying a molecule into its point
e, Cl group, and a sheet at the end of this programme gives this.
Y ou will see that the tests at the bottom of the scheme are
We have so far seen the point groups, Duh, Dnd Dn, Cuh, Cnv similar to those used to introduce the nomenclature in this
and C0 • These groups cover many real molecules, even simple programme. The scheme <loes not test for all the symmetry
linear ones which have an infinity-fold axis e.g. elements of a molecule, only certain key ones which enable
•the point group to be found unambiguously.
H H
1 1
C6cv
e CI Have a look at the sheet, and try to follow it through for the
111 Dxh ion:
e
1

There are three additional groups for highly symmetrical

molecules, octahedral molecules belong to the group 0 11 ,
crh ~
Cl
C 2- - stage j
tetrahedral molecules to Td, and icosahedral structures to I11 •
enfl,c~~/ ==-z]n
You must realise that T d refers to the symmetry of the whole
molecule e.g. CH 4 and CC14 both belong to the Td group, but
CHC1 3 <loes not. H

/,, 1
e
(_~ /// v- Cl
C2

What is the point group of CHC1 3? CI CI (c.f. NH,)

CI
c 2
+--stage2
2.21 c,v
Some rather rare molecules possess only two elements of Stage 1 - it is not one of these special groups
symmetry, and these are given a special symbol: Stage 2 - there is a C 2 axis - :. n = 2
Stage 3 - there is no S4 colinear with C2
E and i only C¡
Stage 4 - there are two C2 axes at right angles, there is a
E and cr only C,
horizontal plane.
E and Sn only S0
Many molecules have no symmetry at all (i.e. · their only What point group have you arrived at? (Remember the value
symmetry element is the identity, E. Such molecules belong of n found in Stage 2.)
to the C 1 point group.
B. F
The following are examples of
1
molecules with only one or two e
symmetry elements.
Br /\'H
What are their point groups? CI
32 Programme 2 Point Groups 33

2.23 D2h A simple rule to remember is that any n-fold staggered

structure (like C2 H 6 , Mni(C0)¡ 0 etc) belongs to the
Use the scheme to find the point group of each of the follow- point group Dnd, and you may find it easier simply to
ing: (C, E, F and G are a bit tricky without a model, but remember this rule.
you may get C, F and G right by analogy with ethane as We have said that the symbol represents the POINT
discussed in frames 2.10-2.13). GROUP of the molecule. This is because all the symmetry
o elements of a molecule always pass through one common
CH, H H H ºc c point (sometimes through a line or a plane, but always
A
"-C=C/ B "-C=C/ e oc- Mn-
co'- 1 through a point).

/
H
"-CH, /
CH,
"-CH, -.......c o ·Where is the point for examples A and G above?
0 c-... _. co
Mn
D E .OC_.. j ..__Ca 2.25 A- the centre of the C=C double bond
c G - the Fe atom
o
At this stage, the programme begins to look at what mathe-
matícians call a GROUP. If you have had enough for one

8
F sitting, this is a convenient place to stop, but in any case it is
not absolutely vital for a chemist to know about the rules
defining a group, although I strongly recommend you to
work through the rest of the programme. You should now
be able to classify a molecule into its point group, which is
2.24 A. C2h B. C2v D. C, E. C, F. Dsh G. Dsd absolutely vital to the use of Group Theory, and the test at
the end of the programme tests only this classification.
The hardest of these examples are probably C and G which
are both Dnd molecules. It is often very difficult to see the n The term GROUP has a precise mathematical meaning, and
2-fold axes on such a molecule and you may need to ask the set of symmetry OPERA TIONS of a molecule constitutes
advice on this. Frame 2.11 shows the axes in the case of a a mathematical group. A group consists of a set of members
D 3d molecule. The corresponding diagram, looking down the which obey four rules:
principal 4-fold axis of Mn2(C0) 10 is:
a. The product of two members, and the square of any
member is also a member of the group.
,, b. There must be an identity element.
_e, c. Combination must be assocíative i.e. (AB)C = A(BC).
'• ' ,' ., ,
'----~·<\ ,,:..:,
__• ·;;;'t.,';-.-'- - - - - - (Jd
d. Every member must have an inverse which is also a
member i.e. AA -l = E, the identity, if A is a member,
~~/;~, \~:--._
A - 1 must also be.
,, ......,/ \,"•. . ,,-- --c2
'
,
/
1
1
'
\
'
' N.B. Sorne texts use the word element for the members of a group.
, ,' : \ 'crd
e' : , This convehtion has not been followed here in order to avoid con-
·' O'd C, fusion with the term symmetry element. It is the set of symmetry
operations which form the group.
34 Programme 2 Point Groups 35

Let us take the e 2v group (e.g. H 20) and confirm these rules. 2.26 E e, O" O" '
The group has four operations, E, e,, o-, o-':
E E e2 /J IJ'

/
cr'
e, e, E O" ' O"

O" /J IJ' E e,

O" ' O" ' /J e2 E

We have already seen the effect of combining two operations
in the programme on elements and operations.
Set up the complete multiplicatioh.table for the group opera-
tions (in Programme 1 you used .a little arrow on H to help
do this).
If you did not get this result, look back at the first pro-
gramme, frames 1.29-1.32.
We can see immediately from this table that rules a and b are
true for this set of operations.
What about rule d? What is the inverse of o-', i.e. what multi-
plies with 1J' to give E?

E e2 O" o-' 2.27 a', it is its own inverse, 1 1

C5 rJ = E. This is true for all the
operations of this group.
E
eonsider the e 3 element in a D 3h molecule. What is the
e2 inverse of the e 3 operation, or what operation will bring
the shape back to the starting point (I'd rather you didn't
say e 3 in the opposite direction!).

o-'

e,
-c!_o_ckw-is_e_..,
2
D3

2.28 et i.e. apply the e 3 operation clockwise a further two times.

Thus eje 3 el E. (Remember that this means e 3 fol-
lowed by ej.)
Note particularly that it is the symmetry OPERATIONS,
not the elements which form a group.
eonfirm rule c for the elements e,, IJ, and 1J' of the e,v
group, i.e. work out the effect of (e2o-) 1J' and of e 2 (M').
36 Programme2 Point Groups 37

2.29 (C2 o-)o-' = o-' o-' = E 2.32

C2 (crcr') = C2 C 2 = E

i.e. the operations are associative.

The C 2v point group only has four operations, so 11 1s a P'.

simple matter to set up the group multiplication table.
There is, however, a further feature of groups which can
only be demonstrated by using a rather larger group such
as C 3v. Ammonia belongs to the C 3v group. Can you wríte
_What single operatíon would take P to P '?
down the five symmetry elements of ammonia?
N
2.33
1,\
H H H.
í.e. o-' C 3 = o-" (remember that this means C3 followed by o-'
has the same effect as o-" -we write the operations in reverse
order).
2.30
What happens if we do it the other way round, i.e. what is o-'
What operations do these elemen\s generate? followed by C3 (= C 3o-')?

2.31 E C3 e~ o- o-' o-" (or 3o-)

We can set up the 6 x 6 multiplícation table for these opera-

tions by considering the effect of each operation on a point
such as P in the diagram below, which has the C3 axis
perpendicular to the paper: ·····•..cr

The C 3 andel
operatíons are clockwise

Draw the position of point P after applying C 3 and then o-'

(call the new positíon P').
38 Programme2 Point Groups 39

2.34 cr a" 2.36

)l P'.
•.
.P
·-..

In this case cr'e 3 does not equal e 3 cr' -we say that these two i.e.
operations do not eOMMUTE.
U se the effect of the group operati ons on the point P to see
í
3/':;
which of the following pairs of operations commute: .P
•····... CT
e 3 and e¡ cr and e 3 J and J' E and el
e,
. 2
2.35 e 3el =E; i.e. e 3 and e, commute What single operation is the same as cre3 cr?
aC 3 = a'; i.e. cr and e 3 do not commute
ao-' = C3; i.e. J and cr' do not commute
2.37 el. Thus e 3 and el are in the same class.
Ee23 -_ e2.
3, i.e. E and el commute
It should be obvious that E commutes with everything-it does What is the inverse of e,?
not matter if you do nothing before or after the operation!
We will now consider briefly the subject of eLASSES of 2.38 el. Work out the similarity transform of cr by e 3, i.e. decide
symmetry operations. Two operations A and B are in the the operation equivalent to elcrC3.
same class if there is sorne operation X such that:
XAx- 1 = B (x- 1 is the inverse of X, i.e. xx- 1 = E)
We say that Bis the similarity transform of A, and that A and
B are conjugate.
r
Ap
Since any J is its own inverse we can perform a similarity cr' _ .. -- ·-.,. "CT
transformation on the operation e 3 by finding the single
operation equivalent to Je 3cr.
Work out the position of point P after carrying out these
three operations.

e 3 is clockwise
40 Programme 2 Point Groups 41

2.39 e'3ae3 = a " a" 2.40 E

2C3
3C2

2Si
3CYv (all equivalen! but different from CYh)
Thus CY and CY" are in the same class

The complete set of symmetry operations of the C 3v point
group, grouped by classes, is as follows:
E (always in a class by itself)
C3 el · Arrange a set of operations into classes.
(Y a' e/'
The operations are commonly written in classes as:
E 2C¡ 3CY
lt is not nécessary to go through the whole procedure of
working out similarity transformations in arder to group
operations into classes. A set of operations are in the same
class if they are equivalen/ operations in the normally
accepted sense. This is probably fairly evident far the example
above.
'You should now be able to:
State the point group to which a molecule belongs.
Confirm that a set of operations constitutes a group.
The assignment of a molecule to its corree! point group is a
vital preliminary to the use of group theory, and this is the
subject of the test which follows. The other two objectives of
this programme are not tested because it is known in ali cases
that the symmetry operations of a molecu]e do constitute a
group, and the tables (character tables) which are used in
working out problems show the operations grouped by
classes.

The D 3h group (e.g. BCl 3) consists of the operations

'
fYv crv"

Group these operations into their six classes

42 Programme 2 Point Groups 43

Point Groups Test Answers

Classify the following molecules and ions into their point group. Y ou One mark each.
may use molecular models and the scheme far classifying molecules.
l. C2v 8. D6d
2. D2h 9. D3
l. CH,C1 2
3. D3a 10. e,
H H H
2. 'B/ ' B / 4. c,v 11. Ta

H
/'--.._/"
H H 5. C3v. 12. Üh
6. D3h 13. Doch
3. Cyclohexane (chair)
(use a model) 7. e, 14. Coov

To be able to proceed confidently to the next programme you should

4. Cyclohexane {boat) have obtained at least 10 out of 14 on this test, and you should
understand the assignment of the point group in any cases you got
Cl wrong.
5. O= P-----ZÍ
--.c.:: Cl If you are in any doubt about the assignment of point groups, return
F 11. CBr4 to frames 2. 7 to 2.24.
6. F'-i-F 12. SF6
F/ I
F 13. CO2
14. ocs
7.
11-v
'-w_..,
H

8. c:J
~
Cr
(staggered)
"-----.../ ox

9. ox = oxalate (a model .is

almos! essential)

10. (a model is valuable)

44 Programme2 Point Groups 45

Point Groups Systematic Classification of Molecules into

Point Groups
Revision Notes

C = rotation axis i = inversion centre

The set of symmetry operations of any geometrical shape forms a S = improper axis (alternating axis) o- = plane of symmetry
mathematical group, which obeys four rules:
1. Examine for special groups
i. The product of two members of the group, and the square of
any member, is also a member of the group. a. Linear, no o- perpendicular to molecular axis. - C00v
ii. There must be an identity element. ):,. Linear, o- perpendicular to molecular axis - D 00 h
iii. Combination must be associative, i.e. (AB)C = A(BC) c. Tetrahedral - Tct
iv. Every member must have .an. inverse, i.e. if A is a member, d. . Octahedral - Oh
then A- 1 must also be a member, where AA- 1 = E. e. Dodecahedral or icosahedral - Ih
0

Symmetry operations do not necessarily commute, i.e. AB <loes ·noÍ 2. Examine for a Cn axis J
always equal BA. ·
1 1
A molecule can be assigned to its point group by a method which
en present C absent
n 1
<loes not require the listing of all symmetry operations of the mole- Find Cn of highest n o pre¡ent - C5
cule; the method merely involves looking for certain key symmetry ora unique Cn - this axis is then present - e
elements. The symbol formost molecular symmetry groups is in three ~ ~ken to be vertical 1 '
no symmetry elements
parts e.g. ~by convention other than E - C,

3. Examine for S 2n colinear with Cn

These have the following meanings:
S2n present S 2n absent
i. The number indicates the order of the principal (highest No olher symmetry elements
order) axis. This axis conventionally defines the vertical present 1 except i - - S
1
2n
direction.
Other symmetry
ii. The capital letter is D if an n-fold principal axis is accom-
elements present
panied by n two-fold axes at right angles to it; otherwise the

iii.
letter is C.
The small letter is h if a horizontal plane is present. If n
-------4. Examine for n horizontal c2 axes
vertical planes are present, the letter is v for a C gtoup but n C2 axes present n C2 axes absent
1
d (= dihedral) for a D group. (N.B. h takes precedence over v Horirntal plane (Oh) present-D0 h Horizóntal plane (6h)
or d.) If no vertical or horizontal planes are present, the small present - Cnh
1
letter is omitted. n Vertical planes (dihedral planes, n vertical planes present
dd, bisecting angles between c axes)
present-D d
2 (6v)"" cm
1 n
Al:isent-D0 Absent-C0
 Non-degenerate Representations 47

Non-degenerate Representations

3.1 What are the point groups of the following molecules?

Programme3
c.
N
Non-degenerate /f'"'
H H H
Representations

3.2 A.· D,h

Objectives
After completing this programme you should be able to:
l. Forma non-degenerate representation to describe the effect
of the symmetry operations of a group on a direction such
as x.
2. Reduce a reducible representation to its componen! irredu-
cible representations.
Both objectives are tested at the end of the programme.
B. C3h
c. c,v
If yo u are quite happy about point groups, continue with this
programme, if not, return to Programme 2 - Point Groups.
We are now going to progress one stage further in the quan-
titative description of molecular symmetry by using numbers
to represen! symmetry operations. These numbers are called
REPRESENTATIONS (not unreasonably!),and in this pro-
grarnme we shall be rnainly concerned with the numbers +1
and -1 so your maths should not be strained too far!

We shall initially use atomic p orbitals to illustrate the

Assumed Knowledge
A knowledge of the shapes of p and d atomic orbitals, and of the
contents of Programmes 1 and 2 is assumed.
features of representations, but you mus! remember that
the features we discover apply to many other directional
properties as well.
Let us look at the effect on a Px orbital of a C2 rotation about

-ep-,
the z axis:
z
e,

The sign of the Px orbital is changed, so how can the opera-

tion be represented, by + 1 or -1?
48 Programme 3 Non-degenerate Representations 49

3.3 -l. Px becomes -Px or: 3.7 + 1

C2Px = -lp,
Let us !ook at the effect of various reflections on the Px
orbital - consider first a reflection in the xz plane which
passes through the orbital:
We have now !ooked at the numbers representing the four
operations E C 2 cr(xz) cr(yz).
These four operations form a group, can you remember
which one it is?

3.8 c,v
·we say that the four numbers form the B1 represeutation of
the C2v group:
What <loes the orbital look like after applying the cr(xz)
operation? E e, cr(xz) cr(yz)

-1 -1 X
3.4 Just the same, because the plane passes through the middle of
both lobes.
Don't worry at this stage about the nomenclature B1 - the
What number will represen! the operation cr(xz)? symbol <loes carry information, but you can regard it simply
as a !abe! for the present.

3.5 +1 i.e. cr(xz) Px = lpx We also say that x belongs to the B1 representation of C 2v
because this set of numbers represents the effect of the group
What about the reflection in the yz plane - what is the result operations on a p, orbital, or indeed anything with the same
of cr(yz)px, and hence what number represents cr(yz)? symmetry properties as the x axis.

If our set of numbers represents the group operations, it

should also represen! the way the group operations combine
together. Use a little arrow on the water molecule to find the
product of the two operations C 2 and cr(xz) like you did in an
earlier programme:
z
3.6 cr(yz)p, = -p,, hence cr(yz) is represented by -1:
y

~
~x~~x
crfy,)~
- - - ~ : : : : . __ _ X

H .....-,H
What number represents the effect of the identity operation,
E?
e,