CHEM 2060 Lecture 3: Symmetry L3-1

Benzene, C6H6 : d mirror plane

WARNING: Differentiating between a v and a d mirror plane can
be a little tricky at first, but with practice it should become clear.
Both v and a d mirror planes are collinear with the principle rotation axis
BUT it is only possible to have a dihedral mirror plane in a molecule in
which EITHER the principle axis Cn
OR an improper rotation axis Sn is 4-fold or larger (n 4)

In a molecule that has both v and a d mirror planes, the v planes bisect as
many atoms as possible and the d planes bisect as many bonds as possible.

CHEM 2060 Lecture 3: Symmetry L3-2

d mirror plane contd

NOTE: Some molecules have only d planes!!
These are molecules in which there is an S2n improper rotation
collinear with the principle Cn axis (see next page).
Molecules belonging to the point group Dnd (see ahead) have only d planes.
Molecules belonging to the point group Oh (see ahead) have h & d planes.
NOTE: d planes are always collinear with the principle axis.

Okay, so what is an improper rotation? (Turn the page!)

CHEM 2060 Lecture 3: Symmetry L3-3

Improper rotations, Sn
An improper rotation consists of a rotation followed by a reflection
in the plane perpendicular to the rotation axis.

Methane, CH4 : S4

NOTE: Neither C4 nor the is a symmetry operator of methane but their

product C4 is (i.e. S4).

CHEM 2060 Lecture 3: Symmetry L3-4

NOTE:
S1 = reflection
S2 = i
Pictorially

So now we need to look at inversion i.

CHEM 2060 Lecture 3: Symmetry L3-5

Inversion Center, i
A center of inversion is a point in the middle of the molecule
(object). If you take each atom and move it through that point from
its original position to the same distance on the other side of the
center of inversion, the molecule appears unchanged.
Hexafluoroantimonate, SbF6- : i

Now you should check for yourself that S2 is indeed the same things as i.

CHEM 2060 Lecture 3: Symmetry L3-6

OK, Thats it: We can now identify molecules by their symmetry elements.
E

Cn

(h, v, d)

Sn

Whether or not a molecule has all or some of these symmetry elements can
easily be classified by assigning a label.
This label identifies the POINT GROUP of the molecule.
There are many, many Point Groups possible, but only a handful are common
for molecular structures.
Some of the most common points that you will be seeing include:
C2v (which describes water, H2O)
C3v (which describes ammonia, NH3)
Td (tetrahedral, which describes methane CH4)
D2h (which describes ethylene, H2CCH2)
Oh (octahedral, which describes sulfur hexafluoride, SF6)

CHEM 2060 Lecture 3: Symmetry L3-7

Assigning Point Groups

VERY IMPORTANT!

Assigning a point group to a molecule depends on listing the symmetry elements

of the molecule and then looking them up in a table.
It is often easier (at first) to work through a YES/NO DECISION TREE.
Obviously, this can be
tedious and eventually
unnecessary as you
become more
comfortable with the
concept.
Eventually, youll be
able to see the
symmetry and assign
the point group without
a decision tree.

CHEM 2060 Lecture 3: Symmetry L3-8

Decision Tree For Assigning Point Groups

From
(a)

Molecule

(a)

(b)

Y Linear

N
Cn? N
Y

Y i ?

Two or
Y more
Cn , n>2
?

Select C n with
Y highest n i then, is
nC 2 Cn ?

Y i ? N

Y i ? N

Ih

Linear groups

Td
Cubic groups

nv? Y

Dnh

Dnd

S2n?

Oh

C v

h?

nd? N

Go to
(b)

Y C? N
5

D h

Y ?
h

Dn

N
Cn

Y
S2n
Cnv

Cnh

Cs

Ci

Cl

CHEM 2060 Lecture 3: Symmetry L3-9

Lets do an example: water, H2O

Start at Top of Tree
Linear NO
Two or more Cns, n > 2 NO
Cn YES (H2O has a C2 rotation axis; n = 2)
Select Highest Cn. Is nC2 Cn?
(In other words, are there 2 more C2 axes perpendicular to the C2 axis?) NO

h NO
n vs

YES
(H2O has two vertical mirror planes; 2 vs)

Cnv because weve identified n = 2 for water, the answer is C2v

CHEM 2060 Lecture 3: Symmetry L3-10

Lets try an example by identifying the symmetry elements: ammonia, NH3

Molecule possesses:
Identity (E)
C3 axis
3

v planes

C3v

or go through tree
Linear ? no,

2 or more Cn no

Cn ? yes, C2 C3 ? no

h ? no,

nv ? yes

Cnv
(n = 3)

Point Group for NH3 is C3v

CHEM 2060 Lecture 3: Symmetry L3-11

Be careful with h and v !

In both examples so far we had to answer questions concerning the minor
planes. Is it h or v?

hs are to the main rotation axis.

vs are to the main rotation axis.

H 2O

E, C2, 2v

CHEM 2060 Lecture 3: Symmetry L3-12

Lets try another example, boron trifluoride, BF3 :

Linear ? NO

2 or more Cn (n > 2)? NO

Cn ? YES (C3

i.e., n = 3)

F
B
F

Are there 3 C2 C3 ? YES

h ? YES

Dnh

and because n = 3, the point group for BF3 is D3h

HOMEWORK FOR TUTORIAL: Prove that BF3 and PCl5 have the same point
group.

CHEM 2060 Lecture 3: Symmetry L3-13

More
examples:

C
One infinite-fold rotation axis with infinite number of symmetry planes
which include the rotation axis.
D2 Three mutually perpendicular 2-fold rotation axes.
D3 One 3-fold rotation axis and three 2-fold rotation axes perpendicular to the
3-fold axis.
C

D2

D3

CHEM 2060 Lecture 3: Symmetry L3-14

Summary of the truth table

There are only 2 linear groups, either Dh or Cv . (Question: Why no others?)
If there are multiple Cn axes where n > 2, it is one of the cubic groups: Ih, Oh, Td
Search for the highest order Cn axis
if there are C2 axes D
if there are NO C2 C

(with the exception of S2n)

(This is the difference between D & C)

For D groups
If

D and

h Dnh (See later ds bisect C2s)

d Dnd (ds bisect C2s)
NO Dn