Element
Operation
Symbol
Identity
Identity
Proper axis
Rotation by (360/n)
Cn
Improper axis
1. Rotation by (360/n)
2. Reflection in plane perpendicular to rotation axis
Sn
(-x,-y,-z).
C2H6
Ru(CO)6
C4H4Cl2F2
Identity (E)
Simplest symmetry operation. All molecules have this element. If the
molecule does have no other elements, it is asymmetric.
The identity operation amounts to doing nothing to a molecule and
so leaves any molecule completely unchanged.
CHFClBr
SOFCl
Successive Operations
HCl
C v
F2
Dh
Tetrahedral Geometry
P4
Octahedral Geometry
[W(CO)6]
B4Cl4
Icosahedral Geometry
[B12H12]2
10
11
Cn Point Groups
Cnn = E
PBrClF
C1
H2O2
C2
As(C6H5)3
C3
M(NH2CH2CO2)4 C4
HOCl
NH2F
BBrClF
N2F2
C2h
B(OH)3
C3h
12
H2O
SF4
C2v
C2v
NF3
SF5Cl
CHCl3
C3v
C3v
C4v
There must be n
C2 axes
perpendicular to
Cn
D2
D3
C2H4
D2h
[PtCl4]2D4h
13
BF3
D3h
D2d
Ferrocene
Fe(C5H5)2
D5d
14
Sn groups
For odd n, (Sn)n = h
For even n, (Sn)n = E
The Sn for odd n is the same as the Cnh.
1,3,5,7-tetrafluorocyclooctatetraene
Linear Groups
H-Cl
O=O
Cv
Dh
Has a h
CCl4
SF6
C60
Td
Oh
Ih
15
The letter A.
GeH3F
tetrachloroplatinate(II)
SF6
HOCl
H
SeH3F
B(OH)3
B
H
O
BH3
Crown-shaped S8
Ni(en)3
16
17
Character Tables
Character tables contain, in a highly symbolic form, information
about how something of interest (an bond, an orbital, etc.) is affected
by the operations of a given point group.
Each point group has a unique character table, which is organized
into a matrix.
Column headings are the symmetry operations, which are grouped
into classes.
Horizontal rows are called irreducible representations of the point
group.
The main body consists of characters (numbers), and a section on
the right side of the table provides information about vectors and
atomic orbitals.
C2v
E C2 v(xz) v(yz)
A1
1 z
A2
-1
1 Rz
xy
B1
-1
1 x, Ry
xz
B2
1 1
1 y, Rx
yz
C3v
E 2C3
A1
1 z
A2
-1 Rz
-1
x2, y2, z2
3v
x2 + y2, z2
Symmetry elements possessed by the point group are in the top row
Left hand column gives a list of symmetry labels
Gives information about degeneracies (A and B indicate nondegenerate, E refers to doubly degenerate, T means triply
degenerate)
Main part of table contains characters (numbers) to label the
symmetry properties (of MOs or modes of molecular vibrations)
18
To obtain from this total set the representations for vibration only, it
is necessary to subtract the representations for the other two forms
z
of motion: rotation and translation.
z
O y
z
y
x
x
Cartesian displacement vectors for a water molecule
Translational Modes
Rotational Modes
A mode in which
all atoms are
moving in the
same direction,
equivalent to
moving the
molecule.
A mode in which
atoms move to
rotate (change
the orientation
of) the molecule.
There are 3
rotational modes
for nonlinear
molecules, and 2
rotational modes
for linear
molecules.
19
20
C2v
E C2 v(xz) v(yz)
A1
1 z
A2
-1
1 Rz
xy
B1
-1
1 x, Ry
xz
B2
1 1
1 y, Rx
yz
x2, y2, z2
C2v
E C2 v(xz) v(yz)
A1
1 z
A2
-1
1 Rz
xy
B1
-1
1 x, Ry
xz
B2
1 1
1 y, Rx
yz
x2, y2, z2
21
D 3h
2C 3
3C 2
hh
2S 3
A 1
3
3
vv
1
A2
1
2
1
-1
-1
0
1
2
1
-1
-1
0
1
1
2
1
1
-1
1
-1
0
-1
-1
-2
-1
-1
1
-1
1
0
E
A 1
A2
E
x 2 + y 2, z 2
Rz
(x , y )
(x 2 y 2, 2xy )
z
(R x , R y ) (xy , yz )
22
The vibrational modes of CH4 (Td), only two of which are IR active.
CCl4
http://fy.chalmers.se/OLDUSERS/brodin/MolecularMotions/CCl4spectra.html
23
24
25
Enantiometers
26
Group Theory
Supplemental Material
C2
(xz)
(yz)
x
Coordinates are assigned according to the convention that the highest
fold axis of rotation is aligned with the z-axis, and the x axis is
perpendicular to the plane of the molecule.
Let the translation of the molecule in the +y direction be represented
by unit vectors on the atoms, and consider how they change when
undergoing the C2v symmetry operations.
O
O
O
O
z
H
E
H
y
x
O
H
B2
H
+1
H
C2
v (xz)
O
H
H
-1
O
-1
v (yz)
O
H
H
+1
27
The set of four labels (+1, -1, -1, +1) generated in the analysis
constitutes one irreducible representation within the C2v point
group. It is irreducible in the sense that it cannot be decomposed
into a simpler or more fundamental form.
Not only does it describe the effects on the y translation but also
on other y-vector functions such as a py orbital.
Therefore, y is understood to serve as a basis function for this
irreducible representation within the C2v point group.
Effect of a symmetry rotation about the z-axis.
H
E
H
C2
v (xz)
v (yz)
y
x
O
A2
H
+1
H
H
+1
O
H
H
H
-1
-1
+1
v (yz)
O
H
-1
v (xz)
O
H
H
=
H
C2
B1
O
H
H
+1
H
-1
H
E
O
H
C2
O
H
v (xz)
v (yz)
y
x
O
A1
H
+1
O
H
H
+1
O
H
H
+1
H
+1
28
C2v
E C2 v(xz) v(yz)
A1
1 z
A2
-1
1 Rz
xy
B1
-1
1 x, Ry
xz
B2
1 1
1 y, Rx
yz
x2, y2, z2
Reducible Representations
When applying the methods of group theory to problems
related to molecular structure or dynamics, the procedure
that is followed usually involves deriving a reducible
representation for the phenomenon of interest, such as a
molecular vibration, the then decomposing it into its
irreducible components.
A reducible representation will always be a sum of
irreducible representations.
In some cases (simple molecules with few bonds) we can
perform the decomposition by inspection, for the more
general case (complicated molecule with many bonds),
we can use the reduction formula.
29
Reducible Representations
The reduction can be achieved using the reduction formula. It is a
mathematical way of reducing that will always work when the answer
cannot be spotted by eye. It is particularly useful when there are
large numbers of bonds involved.
The vibrational modes of the molecule are reduced to produce a
reducible representation into the irreducible representations. This
method uses the following formula reduction formula:
N=
1
rx ix n x
h x
Contribution
per atom*
C2
-1
C3
C4
C6
-3
S3
-2
S4
-1
S6
E
y
y
x
x
z
z
(xz)
y
y
x
x
z
x
i
y
x
y
z
30
y
x
O
Ha
3
Ha
Hb
O
Hb
O
C2
Ha
O
Ha
1
Hb
Hb
(xz)
1
Hb
Hb
O
Ha
Ha
O
(yz)
3
Ha
Hb
Ha
Hb
E
Unshifted Atoms
3
Contribution per atom 3
9
tot
C2
1
-1
-1
v(xz)
1
1
1
v(yz)
3
1
3
31
Reducible Representations
The reduction can be achieved using the reduction formula. It is a
mathematical way of reducing that will always work when the answer
cannot be spotted by inspection. It is particularly useful when there
are large numbers of atoms and bonds involved.
The vibrational modes of the molecule are reduced to produce a
reducible representation into the irreducible representations. This
method uses the following formula reduction formula:
N=
1
rx ix n x
h x
C2
v(xz)
v(yz)
-1
Character Table
2)
irrep
C2v
E C2 v(xz) v(yz)
A1
A2
B1
-1
B2
1 1
1 z
h=4
x2, y2, z2
1 Rz
xy
1 x, Ry
xz
1 y, Rx
yz
N=
1
rx ix n x
h x
(3)(iv(yz))(nv(yz))
32
C2
v(xz)
v(yz)
-1
is resolved into three A1, one A2, two B1, and three B2 species.
C2v
E C2 v(xz) v(yz)
A1
A2
B1
-1
B2
1 1
tot
1 z
x2, y2, z2
1 Rz
xy
1 x, Ry
xz
1 y, Rx
yz
-[trans =
A1
+ B1 + B2]
-[rot
A2 +
vib
= 2A1 + B2
B1 + B2]
33
C2v
E C2 v(xz) v(yz)
Unchanged OH bonds 2
Character
Table
Reducible
Representation
C2v
E C2 v(xz) v(yz)
A1
A2
B1
-1
B2
1 1
x2, y2, z2
1 z
1 Rz
xy
1 x, Ry
xz
1 y, Rx
yz
E C2 v(xz) v(yz)
A1 1
B2 1
-1
-1
Sum of rows 2
C2
v(xz)
v(yz)
Coefficient
Order of group
C2v
E C2 v(xz) v(yz)
A1
A2
B1
-1
B2
1 1
1 z
x2, y2, z2
1 Rz
xy
1 x, Ry
xz
1 y, Rx
yz
34
Derive tot for BCl3 given the character table for D3h
Derive the number of vibrational modes and assign modes for BCl3.
2C3
3C2
2S3
3v
Unshifted atoms
-1
-2
tot
12
-2
-2
D 3h
2C 3
3C 2
hh
2S 3
A 1
3
3
vv
1
A2
1
2
1
-1
-1
0
1
2
1
-1
-1
0
1
1
2
1
1
-1
1
-1
0
-1
-1
-2
-1
-1
1
-1
1
0
E
A 1
A2
E
x 2 + y 2, z 2
Rz
(x , y )
(x 2 y 2, 2xy )
z
(R x , R y ) (xy , yz )
r *i *n
A 1
A 2
E
A 1
A 2
E
12
12
24
12
12
24
0
0
0
0
0
0
-6 4
6 4
0 8
-6 -4
6 -4
0 -8
-4
-4
4
4
4
-4
6
-6
0
-6
6
0
1/h
Sum
Total
0.083333
0.083333
0.083333
0.083333
0.083333
0.083333
12
12
36
0
24
12
1
1
3
0
2
1
tot = A1 + A 2 +3 E+2 A 2 + E
but, subtract off the translational representations.
E + A 2 ]
-[trans =
-[rot =
vib =
E
+
+2 E + A 2 ]
A 2
A1
Each E
representation
describes two
vibrational
modes of equal
energy.
35
Symmetrical
stretching.
Raman active.
Out-of-plane
bending mode.
IR active.
Unsymmetrical
stretching.
In-plane
bending mode.
36
Determine the number of and assign the vibrational modes of the following:
How many peaks in the (1) IR spectra and (2) Raman spectra
1. NH3
2. CH4
3. [PtCl4]24. SF6
5. SF5Cl
Determine number of CO stretching modes in
1. Mn(CO)6
2. Mn(CO)5Cl
3. trans-Mn(CO)4Cl2
4. cis-Mn(CO)4Cl2
5. fac-Mn(CO)3Cl3
6. mer-Mn(CO)3Cl3
37