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Chem 59-651
Symmetry and Introduction to Group Theory
The term symmetry is derived from the Greek word symmetria which
means measured together. An object is symmetric if one part (e.g. one
side) of it is the same* as all of the other parts. You know intuitively if
something is symmetric but we require a precise method to describe how
an object or molecule is symmetric.
Chem 59-651
We need to be able to specify the symmetry of molecules clearly.
F
No symmetry CHFClBr
Cl
Br
Cl
Cl
Cl
Cl
Cl
What about ?
Operation
Rotation axis, Cn
n-fold rotation
Plane of symmetry,
Reflection
Center of symmetry, i
Inversion
Identity, E
Chem 59-651
n-fold rotation - a rotation of 360/n about the Cn axis (n = 1 to )
180
O(1)
H(3)
H(2)
O(1)
H(3)
H(2)
H(2)
H(4)
120
120
N(1)
N(1)
H(4)
H(3)
H(2)
N(1)
H(4)
H(3)
H(2)
Chem 59-651
Notes about rotation operations:
- Rotations are considered positive in the counter-clockwise direction.
- Each possible rotation operation is assigned using a superscript integer m
of the form Cnm.
- The rotation Cnn is equivalent to the identity operation (nothing is moved).
H(3)
H(2)
H(4)
C32
C31
N(1)
H(2)
N(1)
H(4)
H(4)
N(1)
H(3)
H(2)
C3 3 = E
N(1)
H(4)
H(3)
H(3)
H(2)
Chem 59-651
Notes about rotation operations, Cnm:
- If n/m is an integer, then that rotation operation is equivalent to an n/m fold rotation.
e.g. C42 = C21, C62 = C31, C63 = C21, etc. (identical to simplifying fractions)
Cl(2)
Cl(5)
Cl(3)
C4 1
Cl(2)
Ni(1)
Cl(3)
C42 = C21
Cl(4)
Ni(1)
Cl(5)
Cl(3)
Cl(4)
Cl(4)
Ni(1)
Cl(5)
Ni(1)
Cl(2)
C4 3
Cl(3)
Cl(5)
Cl(2)
Cl(4)
Chem 59-651
Notes about rotation operations, Cnm:
- Linear molecules have an infinite number of rotation axes C because any
rotation on the molecular axis will give the same arrangement.
C(1)
O(2)
O(2)
C(1)
O(3)
C(1)
O(2)
N(2)
N(1)
N(1)
N(2)
Chem 59-651
The Principal axis in an object is the highest order rotation axis. It
is usually easy to identify the principle axis and this is typically
assigned to the z-axis if we are using Cartesian coordinates.
Ethane, C2H6
Benzene, C6H6
Chem 59-651
O(1)
H(3)
H(2)
H(3)
H(2)
O(1)
H(2)
O(1)
H(3)
O(1)
H(2)
H(3)
Chem 59-651
Notes about reflection operations:
- A reflection operation exchanges one half of the object with the reflection of
the other half.
- Reflection planes may be vertical, horizontal or dihedral (more on d later).
- Two successive reflections are equivalent to the identity operation (nothing is
moved).
h
A horizontal mirror plane, h, is
Chem 59-651
Cl 2
2F
Br 2
Cl 1
Br 1
1 Br
2 Br
1 Cl
2 Cl
F1
i
[x, y, z]
We will not consider the matrix approach to each of the symmetry operations in this
course but it is particularly helpful for understanding what the inversion operation
does. The inversion operation takes a point or object at [x, y, z] to [-x, -y, -z].
Chem 59-651
F1
F4
F1
S 41
F2
F3
H1
H4
F3
F2
F4
F1
90
H2
H3
S41
H2
H1
H3
C21
H4
F3
F4
S42
H3
H2
H4
H1
Chem 59-651
Chem 59-651
Chem 59-651
Special cases:
Perfect tetrahedral (Td) e.g. P4, CH4
Chem 59-651
F2
F3
Cl
Cl
Chem 59-651
Cl
Br
Br
Cl
No symmetry (C1)
e.g. CHFClBr
F
Cl
Br
Chem 59-651
Cn type groups:
A Cn axis and a h (Cnh)
e.g. B(OH)3 (C3h, conformation is important !)
H
O
Note: molecule does not have to be planar e.g. B(NH2)3 (C3h, conformation is important !)
Chem 59-651
Cn type groups:
Only a Cn axis (Cn)
e.g. B(NH2)3 (C3, conformation is important !)
H
H
N
H
N
Chem 59-651
Cn type groups:
A Cn axis and a v (Cnv)
e.g. NH3 (C3v)
H
Chem 59-651
Cn type groups:
A Cn axis and a v (Cnv)
e.g. NH3 (C3v, conformation is important !)
e.g. carbon monoxide, CO (Cv)
H
H
Cl
F
Sb
Sb
Br
Cl
O
C
F
Br
Chem 59-651
Dn type groups:
A Cn axis, n perpendicular C2 axes
and a h (Dnh)
e.g. BH3 (D3h)
H
Cl(4)
Ni(1)
Cl(3)
Cl(5)
B
H
Chem 59-651
Dn type groups:
O
C
Chem 59-651
Dn type groups:
A Cn axis, n perpendicular C2 axes
and no mirror planes (Dn)
-propellor shapes
e.g. Ni(CH2)4 (D4)
H
H
H
H
Ni
H
H
H
H
Ni
H
Ni
H
Chem 59-651
e.g. (SCH2CH2)3 (D3 conformation is important!)
Chem 59-651
Dn type groups:
A Cn axis, n perpendicular C2 axes
and a d (Dnd)
e.g. ethane, H3C-CH3
H
H
H
H
dihedral means between sides or planes this is where you find the C2 axes
Chem 59-651
e.g. Mg(5-Cp)2 and other metallocenes in the staggered conformation (D5d)
Fe
Mg
Al
e.g. triagular
antiprism (D3d)
e.g. square
antiprism (D4d)
Chem 59-651
C2V
C2
v (xz)
v (yz)
A1
A2
-1
-1
B1
-1
-1
B2
-1
-1
Character
Representation of B2
Representations are subsets of the complete point group they indicate the
effect of the symmetry operations on different kinds of mathematical
functions. Representations are orthogonal to one another. The Character is
an integer that indicates the effect of an operation in a given representation.
Symmetry of Functions
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
y
E
C2
v (xz)
v (yz)
No change
symmetric
1s in table
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
v (xz)
No change
symmetric
1s in table
y
C2
Opposite
anti-symmetric
-1s in table
v (yz)
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
y
E
v (yz)
No change
symmetric
1s in table
y
C2
Opposite
anti-symmetric
-1s in table
v (xz)
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
x
No change
symmetric
1s in table
E
C2
v (xz)
v (yz)
Opposite
anti-symmetric
-1s in table
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
x
No change
symmetric
1s in table
E
C2
v (xz)
v (yz)
Opposite
anti-symmetric
-1s in table
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
No change
symmetric
1s in table
y
E
C2
v (xz)
v (yz)
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
D3h
2 C3
3 C2
2 S3 3 v
A1
A2
-1
-1
Rz
-1
-1
(x,y)
A1
-1
-1
-1
A2
-1
-1
-1
-1
-2
(Rx, Ry)
x2 + y2, z2
(x2 - y2, xy)
(xz, yz)
2 C3
3 C2
2 S3 3 v
A1
A2
-1
-1
Rz
-1
-1
(x,y)
A1
-1
-1
-1
A2
-1
-1
-1
-1
-2
(Rx, Ry)
x2 + y2, z2
(x2 - y2, xy)
(xz, yz)
+0.87
+1
-1
C2 (x)
(+1) + (-1) = 0
C3
sin(120) = 0.87
-0.5
-0.87
-0.5
8 C3
6 C2
6 C4
3 C2
(C42)
6 S4
8 S6
3 h
6 d
A1g
A2g
-1
-1
-1
-1
Eg
-1
-1
T1g
-1
-1
-1
-1
T2g
-1
-1
-1
-1
A1u
-1
-1
-1
-1
-1
A2u
-1
-1
-1
-1
-1
Eu
-1
-2
-2
T1u
-1
-1
-3
-1
T2u
-1
-1
-3
-1
x2 + y2 + z2
(2z2 - x2 - y2,
x2 - y2)
(Rx, Ry, Rz)
(xz, yz, xy)
(x, y, z)
C2V
C2
v (xz)
v (yz)
Cl
Cl
C2V
C2
v (xz)
v (yz)
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
C2
v (xz)
v (yz)
C2V
C2
v (xz)
v (yz)
A1
x2,y2,z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
The formula to figure out the number of symmetry representations of a given type is:
1
o rd e r
o f o p e r a t io n s in c la s s ( c h a r a c t e r o f R R ) c h a r a c t e r o f X
1
1 4 1 1 0 1 1 2 1 1 2 1
4
1
1 4 1 1 0 1 1 2 1 1 2 1
nB1
1
1 4 1 1 0 1 1 2 1 1 2 1
4
nB2
1
1 4 1 1 0 1 1 2 1 1 2 1
The point group is D3h so we must use the appropriate character table to
find the reducible representation of the sigma bonding, first, then we can
go the representation of the bonding, . To determine all we have to
do is see how each symmetry operation affects the 3 bonds in the
molecule.
The E and the h operations leave everything where it is so all three bonds
stay in the same place and the character is 3 (1+1+1).
The C3 and S3 operations move all three bonds so their characters are 0.
The C2 operation moves two of the bonds and leaves one where it was so
the character is 1.
Each v operation leaves one bond where it was and moves two bonds so
the character is 1.
Overall, the reducible representation for the sigma bonding is:
D3h
2 C3
3 C2
2 S3 3 v
0
Chem 59-651
n
n
D3h
2 C3
3 C2
2 S3 3 v
0
D3h
2 C3
3 C2
2 S3
3 v
A1
A2
-1
-1
Rz
-1
-1
(x,y)
A1
-1
-1
-1
A2
-1
-1
-1
-1
-2
(Rx, Ry)
1
x2 + y2, z2
(x2 - y2, xy)
(xz, yz)
A '1
1
12
1 3 1 2 0 1 3 1 1 1 3 1 2 0 1 3 1 1
A '2
1
12
1 3 1 2 0 1 3 1 1 1 3 1 2 0 1 3 1 1
A '1
A '2
12
1
12
0
12
1
12
1 3 2 2 0 1 3 1 0 1 3 2 2 0 1 3 1 0 n E '
1
12
12
We can stop here because the combination (A1 + E) produces the that we determined. None
of the other representations can contribute to the bonding (i.e. nA1, nA1 and nE are all 0). The
irreducible representation (A1 + E) shows us that the orbitals involved in bonding are the s and
nE'
S
O
1)
Pi bonds change sign across the inter-nuclear axis. We must consider the
effect of the symmetry operation on the signs of the lobes in a bond.
2)
There is the possibility of two different type bonds for any given bond
(oriented 90 from each other). We must examine each of these.
This means that we have to find reducible representations for both the
system perpendicular to the molecular plane (, vectors shown in red) and
the pi system in the molecular plane (// , vectors shown in blue).
O
S
O
h ,C2
The C3 and S3 operations move all three vectors so their characters are
0.
The C2 operation moves two of the vectors and reverses the sign of the
other one so the character is -1.
The h operation reverses the sign of all three vectors so the character
is -3.
Each v operation leaves one vector where it was and moves the two
others so the character is 1.
Overall, the reducible representation for the perpendicular bonding is:
D3h
2 C3
3 C2
-1
-3
2 S3 3 v
0
Chem 59-651
A '1
A ''2
D3h
2 C3
3 C2
-1
-3
2 S3 3 v
D3h
2 C3
3 C2
2 S3
3 v
A1
A2
-1
-1
Rz
-1
-1
(x,y)
A1
-1
-1
-1
A2
-1
-1
-1
-1
-2
(Rx, Ry)
1
x2 + y2, z2
(x2 - y2, xy)
(xz, yz)
1
12
1 3 1 2 0 1 3 1 1 1 3 1 2 0 1 3 1 1
1
12
1 3 1 2 0 1 3 1 1 1 3 1 2 0 1 3 1 1
A '1
A ''2
0
12
12
1
12
1
12
1 3 2 2 0 1 3 1 0 1 3 2 2 0 1 3 1 0
n E ''
1
12
12
Going through all the possibly symmetry representations, we find that the combination (A2 + E)
produces the that we determined. The irreducible representation shows us that the possible
orbitals involved in perpendicular bonding are the pz and the dxz and dyz pair. This is in
agreement with the bonding we would predict using VBT.
n E ''
v ,C2
The C3 and S3 operations move all three vectors so their characters are
0.
The C2 operation moves two of the vectors and reverses the sign of the
other one so the character is -1.
Each v operation reverses the sign one vector where it was and
moves the two others so the character is -1.
Overall, the reducible representation for the parallel bonding is:
D3h
2 C3
3 C2
//
-1
2 S3 3 v
0
-1
Chem 59-651
n
n
D3h
2 C3
3 C2
//
-1
2 S3 3 v
D3h
2 C3
3 C2
2 S3
3 v
A1
A2
-1
-1
Rz
-1
-1
(x,y)
A1
-1
-1
-1
A2
-1
-1
-1
-1
-2
(Rx, Ry)
-1
x2 + y2, z2
(x2 - y2, xy)
(xz, yz)
A '1
1
12
1 3 1 2 0 1 3 1 1 1 3 1 2 0 1 3 1 1
A '2
1
12
1 3 1 2 0 1 3 1 1 1 3 1 2 0 1 3 1 1
A '1
A '2
0
12
12
1
12
1
12
1 3 2 2 0 1 3 1 0 1 3 2 2 0 1 3 1 0 n E '
1
12
12
Going through all the possibly symmetry representations, we find that the combination (A2 + E)
produces the // that we determined. The possible orbitals involved in parallel bonding are only
the dx2-y2 and dxy pair. The A2 representation has no orbital equivalent. Note: Such analyses do
NOT mean that there is bonding using these orbitals it only means that it is possible
based on the symmetry of the molecule.
nE'
The point group is Td so we must use the appropriate character table to find
the reducible representation of the sigma bonding, first, then we can go
the representation of the bonding, .
The E operation leaves everything where it is so all four bonds stay in the
same place and the character is 4.
Each C3 operation moves three bonds leaves one where it was so the
character is 1.
The C2 and S4 operations move all four bonds so their characters are 0.
Each d operation leaves two bonds where they were and moves two bonds
so the character is 2.
Td
8 C3
3 C2
6 S4 6 d
0
Cl
O
Chem 59-651
Td
8 C3
3 C2
6 S 4 6 d
Td
8 C3
3 C2
6 S4
6 d
A1
A2
-1
-1
-1
T1
-1
-1
T2
-1
-1
(x, y, z)
x2 + y2 + z2
The irreducible representation for the bonding is (A1 + T2), which corresponds
to the s orbital and the (px, py, pz) set that we would use in VBT to construct a the
sp3 hybrid orbitals suitable for a tetrahedral arrangement of atoms. To get the
representation for the bonding, we must do the same procedure that we did for
SO3, except that in the point group Td, one can not separate the representations
into parallel and perpendicular components. This is because the three-fold
symmetry of the bond axis requires the orthogonal
vectors to be treated as an inseparable pair.
Td
8 C3
3 C2
-1
6 S4 6 d
0
Td
8 C3
3 C2
6 S4
6 d
A1
A2
-1
-1
-1
T1
-1
-1
T2
-1
-1
(x, y, z)
x2 + y2 + z2