Chapter1 - Symmetry and Point Group

CBC 212 - Inorganic Chemistry
Asst. Prof. Chen Hongyu and So Cheuk Wai
Textbook:
“Inorganic Chemistry”, 4th Edition
Gary L. Miessler and Donald A. Tarr, Pearson.
Suggested Readings:
“Inorganic Chemistry”, (Textbook of CBC 212 last year),
C. E. Housecroft, and A. G. Sharpe,
2nd Ed., Pearson Education. 2005.
1
CBC 212 INORGANIC AND
BIOINORGANIC CHEMISTRY
Inorganic Chemistry :
International Edition 4th ed
Author : Gary L. Miessler

Donald A. Tarr
Publisher : Pearson
ISBN : 978-0-13-615383-2
Student Solution Manual Available!
2
About me
Asst. Prof. Hongyu Chen (陈虹宇)
B. Sc. 1998 University of Science and Technology of China (中国科技大学)

Ph.D. 2004 Yale University
Post Doc. 2005-6 Cornell University
Asst. Prof. 2006- Nanyang Technological University
Contact:
Office Phone 6316-8795; E-mail: hongyuchen@ntu.edu.sg
My office:
SPMS-CBC-03-Room 02
Office hour: Please call me directly to arrange a time. Schedule a

meeting would take 2-3 e-mails, which costs too much of my time.
3
Tutorials
CBC212 tutorials are on week 3, 5, 7, 10 and 12
I will teach T1 and T4:

Thur 10:30am-11:30pm and 1:30pm-2:30pm
4
What is Inorganic Chemistry?
Inorganic
InorganicChemistry
Chemistrydeals
dealswith
witheverything
everythingthat
thatisisnot
notorganic
organicchemistry.
chemistry. 5
What is Inorganic Chemistry?
Inorganic
InorganicChemistry
Chemistrydeals
dealswith
witheverything
everythingthat
thatisisnot
notorganic
organicchemistry.
chemistry.
Chemistry deals with gases, metals, salts, metal ions, ect.
Coordination Chemistry
Organometallic Chemistry: Bioinorganic Chemistry:

metal-carbon bonds Metal ions that are
important in biology
6
What will we cover?
Chapter 1 ⎯ Simple Bonding Theory (brief overview)

Chapter 2 ⎯ Symmetry and Group Theory Next week
Chapter 3 ⎯ Molecular Orbitals
Solid State Chemistry Æ CBC951

Chapter 6 ⎯ Coordination Chemistry - Structures and Isomers
Chapter 7 ⎯ Coordination Chemistry - Bonding
Chapter 8 ⎯ Coordination Chemistry – Electronic Spectra
Chapter 9 ⎯ Coordination Chemistry – Reactions & Mechanism
Organometallic Chemistry Æ CBC312
Chapter 10 ⎯ Bioinorganic Chemistry
7
What will we cover?
Chapter 1 ⎯ Symmetry and Group Theory

Solid State Chemistry Æ CBC951
Chapter 3 ⎯ Coordination Chemistry - Structures and Isomers

Chapter 4 ⎯ Coordination Chemistry - Bonding
Chapter 5 ⎯ Coordination Chemistry – Electronic Spectra
Chapter 6 ⎯ Coordination Chemistry – Reactions & Mechanism
Organometallic Chemistry Æ CBC312
Chapter 7 ⎯ Bioinorganic Chemistry (maybe)
8
Take note.
Weight of final mark.
⎯⎯ Homework 10%
⎯⎯ Mid-term (~week 8 or 9) 30%
⎯⎯ Final exam 60%
9
Summary

• Symmetry Elements and Operation
• Point Groups
10
Symmetry ⎯⎯ Nomenclature
Symmetry The operation performed on an object which leaves it

Operation in a configuration that is indistinguishable from, and
superimposable on, the original configuration.
Symmetry Geometric entities that are used to manipulate

Elements molecules so as to transform the molecules, such as
points, lines (axis) and planes
Symmetry Group
• Point group ⎯ a group of symmetry elements that leave at least one
common point unchanged (a single object).
• Space group ⎯ translation through space included.
Point Symmetry The symmetry possessed by a single object that

describes the repetition of identical parts of the object.
Space Symmetry The symmetry describing the relationship of different

objects to each other in space
11
Axes of Symmetry
C2 axis is the symmetry element (no movement is involved)

Symmetry operation is the to rotate the molecule according to C2 axis.
BF3 12
Axes of Symmetry
Point symmetry
Space symmetry
13
Symmetry ⎯ identity operator
Identity Î E Identity operation.
This operator leaves the object unchanged.
All molecules possess this symmetry element.
14
Axes of Symmetry
n-fold axis of symmetry Î Cn Rotation operation.
After rotation of 360°/n, the object returns to its original configuration.
Principal axis, or highest order

rotation axis, is defined as the Cn
axis having the largest n.
BF3 15
Axes of Symmetry
× No axis of symmetry.
C2
C2
C2
C2
C2
C3
C2
C3
C3 C3 16
Axes of Symmetry
C3
C3
Chiral molecule
17
Axes of Symmetry
C4
C2
Octahedral center
18
Axes of Symmetry
C6
19
Plane of Symmetry, XeF4
Plane of symmetry Î σv, σh, or σd reflection operation.
After reflection through a plane, the object returns to its original configuration.
σv means vertical plane σh means horizontal plane σd means dihedral plane

(relative to principle axis) (relative to principle axis)
The angle between two intersecting planes is known as the dihedral angle. 20
Plane of Symmetry, XeF4
σv means vertical plane σd means dihedral plane

Contains the principle axis, Contains the principle axis,
usually along bonds and bisects the angle between
two adjacent C2 axes.
Usually bisect bonds
21
The angle between two intersecting planes is known as the dihedral angle.
Symmetry - Examples
22
C6H6
Symmetry - Examples
σv
’
σv
σv or σh?
σv or σh?
23
Center of Symmetry
Center of symmetry Î i Inversion operation.
After reflection through the center of the object, the object returns to
its original configuration.
indistinguishable and
superimposable
indistinguishable but
NOT superimposable
24
Center of Symmetry
Center of symmetry Î i Inversion operation.
√
CO2 SF6 C6H6
×
H2S/H2O cis-N2F2 CH4/SiH4
25
Symmetry
Successive symmetry operation:
C32 = C3 × C3; C33 = C3 × C3 × C3
C32 is a symmetry operation, but not a symmetry element.

26
Improper Axis of Symmetry
Improper axis of symmetry Î Sn Rotation-reflection operation

(Improper rotation)
S4 = C4 ×σh: Individually Cn and σh are not symmetry operation for these molecules.
Successive symmetry operation:
After rotation by 360°/n, followed by reflection CF4/CH4/SiH4
through a plane that is perpendicular to the
rotational axis, the object returns to its original
configuration ( Sn ).
After rotation by 360°/n, followed by inversion
through the center of symmetry, the object
returns to its original configuration ( n ).
27
Symmetry - Examples
• S1 is equivalent to σ
• S2 is equivalent to i
CF4/CH4/SiH4 Staggered form of C2H6
28
Ferrocene
Summary of Point Symmetry
29
Symmetry element & its symbol How the related symmetry operation works
Identity, E (x,y,z) Æ (x,y,z)
Center of symmetry, i (x,y,z) Æ (-x,-y,-z)
Mirror plane, σ (case of σxy) (x,y,z) Æ (x,y,-z)
Proper rotational axis, Cn (z axis) (x,y,z)Æ(xcosα-ysinα,xsinα+ycosα,z); α=2mπ/n
Improper rotational axis, Sn (z axis) (x,y,z)Æ(xcosα-ysinα,xsinα+ycosα,-z); α=2mπ/n
30
Schoenflies Notation vs Hermann Mauguin Notation
31
Symmetry - Examples
A chiral molecule does not have an improper rotation axis, Sn

Mirror
32
Symmetry - Examples

[Ru(NH2CH2CH2NH2)3]2+
33
Symmetry - Examples

34
Symmetry - Examples

• S2 is equivalent to i trans-cyclooctene
1,1'-bi-2-naphthol
35
(BINOL)
cis-cyclooctene
Symmetry - Examples

36
Symmetry - Examples

An exception:
tetrafluoro-spiropentane 37
Summary

• Point Groups
38
Point Groups
Symmetry Group ⎯ all the symmetry elements that describe a molecule.

• Point group ⎯ a group of symmetry elements that leave at least one
common point unchanged (a single object).
• Space group ⎯ translation through space included.
D3h C3v
D6h
C6h
Six C2 axes perpendicular to C6 39

Point Groups
Method 1: list all symmetry elements and match with list characteristic of point group.
40
Point Groups
Method 2: Use a flow chart.
41
Point Groups
There are infinitely many 3D point groups, however, in crystallography the

rotational symmetries of a crystal are limited to 2-fold, 3-fold, 4-fold, and 6-fold.
There are only 32 crystallographic point groups. (see Wikipedia: Crystallographic
restriction theorem)
42
Point Groups
(a) The groups C1, Ci, Cs

• C1 point group : E (identity) only
• Ci point group : E and i
• Cs point group : E and mirror plane σ
C1 point group Cs point group

Ci point group 43
Point Groups
(b) The groups Cn, Cnv, and Cnh

• C2 point group : E, C2 Ex) H2O2
• C2v point group : E, C2, 2σv Ex) H2O
• C3v point group : E, C3, 3σv Ex) NH3
• C∞v point group : linear molecule, no inversion center, Ex) CO, HCN
• C2h point group : E, C2, σh Ex) trans-CHCl=CHCl
• C3h point group : E, C3, σh Ex) B(OH)3
C2 point group
C2h point group C3h point group 44
Point Groups
(c) The groups Dn, Dnh, and Dnd

• Dn point group: n-fold principal axis Cn and n × C2 axis present in
the group
• Dnh point group: group element of Dn + σh
D6 point group D6h point group
45
Point Groups
(c) The groups Dn, Dnh, and Dnd
• Dn point group: n-fold principal axis Cn and n × C2 axis present in
the group
• Dnh point group: group element of Dn + σh
• Dnd point group: Dn elements + n × σd
• D∞h point group: linear molecule + inversion center, Ex) O2, C2H2
Ethane, C2H6 (D3d)

Allene, H2C=C=CH2 (D2d)
46
Viewing of C2 axis
47
Viewing of C2 axis
o
x x
o o
x
x
o o
x
48
Viewing of C2 axis
x x
o o
49
Viewing of C2 axis
x x
o o
50
Viewing of C2 axis
x x
51
Point Groups
52
Point Groups
(d) Highly symmetric groups Td and Oh
Td point group Oh point group
53
Point Groups
Td point group
NOT Td point group
54
Point Groups
55
Point Groups
Oh point group
NOT Oh point group
56
Point Groups
(d) Highly symmetric groups Ih
Icosahedron
57
Point Groups
(d) Highly symmetric groups Ih
Truncated Icosahedron
Icosahedron
58
Point Groups
59
Point Groups
60
Point Groups
61
Point Groups
D3h point group

D3h point group
D2h point group 62

Point Groups
D3 point group
Fe(C5H5)2, staggered Os(C5H5)2, eclipsed
D5d point group D5h point group
63
Common Molecular Symmetries
Td C3v
C3v
Oh D4h
64
D∞h C2v
D3h
C2v D4h
C3v
65
C2v
C4v
D3h
66
Coordination Chemistry ― Bonding
67
Summary

• Point Groups
• Character Table
68
Character Table
A set of symmetry operations form a mathematical group

(group theory) when:
• the result of combination of any two operations is also a member

of the group. This is called the multiplication rule: AB = C
• the multiplication rule is also associative: A(BC) = AB(C)
• the group contains a identity element such that AE = EA
• the inverse element of an entity is also a member AA-1 = E
The order of a group is the number of symmetry operations for

that group.
69
Character Table
• We have learned symmetry elements and operations

• We know how to assign an object to a point group
So, what can we do about this knowledge?

• Mathematical treatment leads to character tables which summarize
the symmetry characteristics of point groups. (read page 92~102)
• The character tables can be used to determine physical properties
(such as polarity and chirality), spectroscopic properties (particularly
useful for Raman spectroscopy and Infrared spectroscopy), and to
construct molecular orbitals.
70
NR- Character Table
Each symmetry operation may be expressed as a transformation matrix:

[New coordinates] = [transformation matrix][old coordinates]
reflection in x = 0 plane. ⎛ x' ⎞ ⎛ −1 0 0⎞ ⎛ x⎞
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ Original
⎜ y'⎟ = ⎜ 0 1 0⎟ × ⎜ y⎟ coordinates
Results of ⎜ z' ⎟ ⎜ 0 0 1⎟ ⎜z⎟
⎝ ⎠ ⎝ ⎠ ⎝ ⎠
transformation. Transformation matrix
The matrices record how the x, y, z coordinates are modified as a result of an

operation. For example, the C2v point group consists of the following operations:
• E: do nothing. Unchanged.
• C2: rotate 180 degrees about the z axis
• σ(xz): y becomes –y
• σ’(yz): x becomes -x The character is defined as the trace of a square matrix
⎛ 1 0 0⎞ ⎛ −1 0 0⎞ ⎛ 1 0 0⎞ ⎛ −1 0 0⎞
⎜ ⎟ ⎜ ⎟⎜ ⎟ ⎜ ⎟
⎜ 0 1 0 ⎟ ⎜ 0 −1 0 ⎟ ⎜ 0 −1 0 ⎟ ⎜ 0 1 0 ⎟
⎜0 0 1⎟ ⎜ 0 0 1⎟ ⎜0 0 1⎟ ⎜ 0 0 1⎟
⎝ ⎠ ⎝ ⎠⎝ ⎠ ⎝ ⎠
E C2 σv (xz): σv’ (yz):
71
A reducible representation: 3 -1 1 1
Character Table
Consider a function: f(x) = x2

σv’ (f(x)) = σv(x2) = (-x)2 = x2 = f(x)
f(x) is an eigenfunction of this reflection operator with an eigenvalue of +1.

This is called a symmetric eigenfunction.
Reflection
Get the same orbital back, multiplied by +1,

s orbital
The s orbital is an eigenfunction of the
z reflection, symmetric with respect to the
reflection. 72
Character Table
Similarly for a function: f(x) = x3
σv’ (f(x)) = -1 * f(x)
f(x) is an eigenfunction of this reflection operator with an eigenvalue of -1.

This is called a antisymmetric eigenfunction.
Reflection
Get the same orbital back, multiplied by

-1. The p orbital is an eigenfunction of the
p orbital reflection, antisymmetric with respect to
z the reflection.
73
Character Table
Character Table of C2v

C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 R2 xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
74
Character Table
Character Table of C2v

C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 R2 xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
75
Character Table
Each point group has a complete set of possible

symmetry operations that are conveniently listed
as a matrix known as a Character Table.
Character 6 Symmetry operations

Name of the 3 classes: E, 2C3, 3σv
point group
C3 v E C3 C32 σ v σ v ' σ ' 'v
Γ1 1 1 1 1 1 1
Γ2 1 1 1 −1 −1 −1
Γ3 2 −1 −1 0 0 0
Irreducible representations
Representations are subsets of the complete point Character under E:
group – they indicate the characters of symmetry Dimension of each of
operations on various functions – like those of 76
irreducible representations
orbitals.
Character Table
C3 v E C3 C32 σ v σ v ' σ ' 'v

Γ1 1 1 1 1 1 1
Γ2 1 1 1 −1 −1 −1
Γ3 2 −1 −1 0 0 0
Notes about symmetry labels (Mulliken Symbols) and characters:

• “A” means symmetric with regard to rotation about the principle axis.
• “B” means anti-symmetric with regard to rotation about the principle axis.
• “E” for dimension = 2 and “T” for dimension = 3.
• Subscript numbers are used to differentiate symmetry labels, if necessary.
• “1” indicates that the operation leaves the function unchanged: it is called “symmetric”.
• “-1” indicates that the operation changes the function’s sign: it is called “antisymmetric”. 77
Character Table
Order = 1 + 2 + 3 =6
• The total number of symmetry operation in the group is called order.

• The number of irreducible representations equals the number of classes.
• The sum of the square of the dimensions of each irreducible representation equals
the order of the group. Æ 12 + 12 + 22 = 6
• Irreducible representations are orthogonal to each other.
For A2 and E Æ 1(1)(2) + 2(1)(-1) + 3(-1)(0) = 0
• A totally symmetric representation exist in the group, with characters of 1 for all
operation. Æ in this case A1
78
Character Table
• dxy, dxz, dyz, as xy, xz, yz

• dx2-y2 behaves as (x2 – y2)
• dz2 behaves as 2z2 - (x2 + y2)
• px, py, pz behave as x, y, z
• s behaves as x2 + y2 + z2 79
(because r = √(x2 + y2 + z2)
Character Table
A set of symmetry operations form a mathematical group

(group theory) when:
• the result of combination of any two operations is also a member

of the group. This is called the multiplication rule: AB = C
• the multiplication rule is also associative: A(BC) = AB(C)
• the group contains a identity element such that AE = EA
• the inverse element of an entity is also a member AA-1 = E
The order of a group is the number of symmetry operations for

that group.
80
NR- Character Table
For example in C2v group:

C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy • AB = C
• A(BC) = AB(C)
B1 1 −1 1 −1 x, R y xz
• AE = EA
B2 1 −1 −1 1 y , Rx yz
• AA-1 = E
C2 × σ v ( xz ) = σ v' ( yz )
E × C2 = C2 × E = C2
1 0 0 1 0 0 1 0 0
=
C2 × C2 = E σ v ×σ v = E 0 -1 0 0 -1 0 0 1 0
0 0 1 0 0 1 0 0 1
81
Character Table
A pz orbital has the same symmetry as an arrow pointing along the z-axis.
z z
≡ y y
E
x C2 x
σv (xz)
σ’v (yz) No change
∴ symmetric
∴ 1’s in table
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
82
Character Table
Rz is the vector of rotation around the z-axis (right-hand rule).
z z
y y
E No change
x C2 x ∴ symmetric
∴ 1’s in table
z z
y y
σv (xz) Opposite
x x ∴ anti-symmetric
σ’v (yz)
∴ -1’s in table
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz 83
B2 1 −1 −1 1 y , Rx yz
Character Table
A px orbital has the same symmetry as an arrow pointing along the x-axis.
z z
y y
E No change
≡ x σv (xz) x ∴ symmetric
∴ 1’s in table
z z
y y
C2 Opposite
x σ’v (yz) x ∴ anti-symmetric
∴ -1’s in table
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz 84
B2 1 −1 −1 1 y , Rx yz
Character Table
d orbital functions can also be treated in a similar way
y y
The z axis is pointing
out of the screen.
So these are
representations of the
view of the dz2 orbital
x x
and dx2-y2 orbital down
the z-axis. No change
y y ∴ symmetric
dz2 ∴ 1’s in table
dx2 - y2 E
C2
x σv (xz) x
σ’v (yz)
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
85
B2 1 −1 −1 1 y , Rx yz
Character Table
Note that the representation of orbital depends on the point group (which
must be correctly identified).
C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
D3h E 2 C3 3 C2 σh 2 S3 3 σv
A’1 1 1 1 1 1 1 x2 + y2, z2
A’2 1 1 -1 1 1 -1 Rz
E’ 2 -1 0 2 -1 0 (x,y) (x2 - y2, xy)
A’’1 1 1 1 -1 -1 -1
A’’2 1 1 -1 -1 -1 1 z
86
E’’ 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
Summary

• Point Groups
• Character Table
1. σ-bonding in a C2v group
2. σ-bonding in a Td group
3. Molecular Vibration in C2v
4. Selected vibrational modes in C2v
87
Application of Character Table H
H
σ bonding in CH2Cl2
Γσ (reducible representation of the sigma bonding) is the characters
of each C2v symmetry operation acting on the 4 σ bonds. A bond Cl
contributes 0 to the character if the symmetry operation moves it Cl
and 1 if it doesn’t. The sums of the 1’s and 0’s for each operation
give the representation of the bonding.
The E operation leaves all 4 bonds unchanged, and the character is

4 (1+1+1+1).
The C2 operation moves all four bonds so the character is 0.
Each σv operation leaves two bonds unchanged and moves the

other two bonds so the character is 2 (1+1+ 0 + 0).
Overall, the reducible representation is thus:

Γσ 4 0 2 2 88
Application of Character Table
This representation is not one of those in the point group, but can be reduced
(factored) into some combination of those that are. This can be done either by
inspection or by the use of a relationship illustrated on the next slide.
Γσ 4 0 2 2

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
Because the character under E is 4, there must be a total of 4 symmetry

representations (sometimes called basis functions) that combine to make Γσ.
Since the character under C2 is 0, there must be two of A symmetry and two of B
symmetry. The irreducible representation is (2A1 + B1 + B2), which corresponds to:
s, pz, px, and py orbitals – the familiar sp3.
Note: highly symmetric spherical s orbitals always are unchanged- characters all89+1.
reducible C2V E C2 σv (xz) σ’v (yz)

representation Γσ 4 0 2 2

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
The formula to figure out the number of symmetry representations of a given type is:
nX =
1
order
∑ ( [
# of operations in class) × (character of RR) × (character of X ) ]
nA1 =
1
4
[ ]
(1)(4)(1) + (1)(0)(1) + (1)(2)(1) + (1)(2)(1) nB1 =
1
4
[
(1)(4)(1) + (1)(0)(−1) + (1)(2)(1) + (1)(2)(−1) ]
nA 2 =
1
4
[
(1)(4)(1) + (1)(0)(1) + (1)(2)(−1) + (1)(2)(−1) ] nB2 =
1
4
[(1)(4)(1) + (1)(0)(−1) + (1)(2)(−1) + (1)(2)(1) ]
Which gives: 2 A1’s, 0 A2’s, 1 B1 and 1 B2. 90
Summary

• Point Groups
• Character Table
91
σ bonding for a tetrahedral molecule (CH4, ClO4-, etc..)
z
Character:
C3 1→3
1
3 →4
4→1
2=2
y
C2 2↔3
1↔4
x
also S4 0
σd 2↔3 2
1,4 move
92
σ bonding for a tetrahedral molecule (CH4, ClO4-, etc.).
The point group is Td so we must use the appropriate character table to find
the reducible representation of the sigma bonding, Γσ first, then we can go
the representation of the π bonding, Γπ.
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 σd operation leaves two bonds where they were and moves two
bonds so the character is 2.
Td E 8 C3 3 C2 6 S4 6 σd
Γσ 4 1 0 0 2 93
Td E 8 C3 3 C2 6 S4 6 σd
Γσ 4 1 0 0 2
Td E 8 C3 3 C2 6 S4 6 σd
A1 1 1 1 1 1 x2 + y2 + z2
A2 1 1 1 -1 -1
E 2 -1 2 0 0 (2z2 - x2 - y2, x2 - y2)
T1 3 0 -1 1 -1 (Rx, Ry, Rz)
T2 3 0 -1 -1 1 (x, y, z) (xy, xz, yz)
Work out by yourself the irreducible representation for the σ bonding.
So, the obvious answer is A1 + T2.

• VB theory of CH4 uses 4 sp3 hybrid C orbitals (although sp3 and sd3 is allowed!)
• MO theory constructs orbitals from the C2s and C2p and proper combinations
of the orbitals from the 4 groups bonded to the central atom carbon
94
Carbon atomic valence orbitals
BONDING (in phase) Combinations of ligand (H) orbitals
95
MO Diagram for CH4
3 degenerate MO’s with

high C2p contributiomn
MO with high C2s contribution
4 H1s orbitals
8 atomic orbitals → 8 MO’s 96
The photoelectron spectrum of CH4 support ionizations from two strongly bonding
MO’s having different C2s and C2p characters, not from a single set of sp3 hybrid
orbitals. Two MO’s delocalized over all 5 nuclei result in 4 equivalent C-H bonds.
97
Summary

• Point Groups
• Character Table
98
Introduction
Electric component (IR or Raman)
Magnetic component (EPR or NMR)
Allowed transitions ↔ Forbidden transitions

Selection rules: In order for matter to absorb photon:
1.) Energy must match.
2.) (For electric interactions) The energy transition must be accompanied by a change in
the electrical center of the molecule so that electrical work can be done.
• Infrared absorption: there must be a change of dipole moment in the molecule as it
vibrates.
• Raman absorption: there must be a change in polarizability during the vibration.99
Introduction
How do you describe the movement of a molecule:

translation, rotation and vibration?
See: http://en.wikipedia.org/wiki/Infrared_spectroscopy
100
In a water molecule, each atom can move in all three

directions, leading to a total of nine transformations.
We view the movement (translation, rotation and
vibration) of the water molecule as the combination of
those vectors.
Æ We are interested in the symmetry of the

transformations.
# of atoms degrees of Translational Rotational Vibrational

freedom modes modes modes
N (linear) 3N 3 2 3N-5
Example 9 3 2 4
3 (HCN)
N (non- 3N 3 3 3N-6
linear)
Example 9 3 3 3
3 (H2O) 101
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
How many vibrational modes belong to each irreducible representation?
You need the molecular geometry (point group) and the character table
Use the translation vectors of the atoms as the basis of a reducible
representation.
Since you only need the trace recognize that only the vectors that are
either unchanged or have become the negatives of themselves by a
symmetry operation contribute to the character.
102
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
Total of vectors Γ= 9 -1 3 1
A reducible representation
103
C2 v E C2 σ v ( xz ) σ 'v ( yz )
Γ = 3A1 + A2 + 3B1 + 2B2 A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
Selection rules: In order for matter to absorb photon:

1.) Energy must match.
2.) (For electric interactions) The energy transition must be accompanied by a change in
the electrical center of the molecule so that electrical work can be done.
• Infrared absorption: there must be a change of dipole moment in the molecule as it
vibrates Æ a normal mode must belong to one of the irreducible representations
corresponding to the x, y, and z vectors.
• Raman absorption: there must be a change in polarizability during the vibration.
Æ a normal mode must belong to the same irreducible representations of the
quadratic functions of x, y, and z vectors (x2, y2, z2, xy, yz, xz, x2-y2, etc.), or one104
of
the rotational functions Rx, Ry, Rz
Symmetric stretch
Antisymmetric stretch
Symmetric bend
IR active
Raman active
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz 105
Summary

• Point Groups
• Character Table
106
Example: C-O stretch in C2v (cis) complex.
and C-O stretch in D2h (trans) complex.
1
ν(CO)
O
L C
C2 M
L C
O
2
E C2 σv(xz) σv(yz)
1 2 O 1 2
O O O
L C L C L C L C
M M M M
L C L C L C L C
O O O O
2 1 2 1
Γ 2 0 2 0
Find: # vectors remaining unchanged after operation.
107
Example: C-O stretch in C2v (cis) complex.
and C-O stretch in D2h (trans) complex.
Isolated vibration Coupled vibrations
108
C2 v E C2 σ v ( xz ) σ 'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y , Rx yz
Γ 2 0 2 0
A1 = 1/4 (1x2x1 + 1x0x1 + 1x2x1 + 1x0x1) = 1
A2 = 1/4 (1x2x1 + 1x0x1 + 1x2x-1 + 1x0x-1) = 0 is both IR and
B1 = 1/4 (1x2x1 + 1x0x1 + 1x2x1 + 1x0x1) = 1 Raman active
B2 = 1/4 (1x2x1 + 1x0x1 + 1x2x-1 + 1x0x1) = 0 109

Γ 2 0 0 2 0 2 2 0
110
Summary

• Point Groups
• Character Table
111

Chapter1 - Symmetry and Point Group

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CBC 212 - Inorganic Chemistry

Asst. Prof. Chen Hongyu and So Cheuk Wai

Author : Gary L. Miessler

Asst. Prof. Hongyu Chen (陈虹宇)

B. Sc. 1998 University of Science and Technology of China (中国科技大学)

Office hour: Please call me directly to arrange a time. Schedule a

CBC212 tutorials are on week 3, 5, 7, 10 and 12

I will teach T1 and T4:

Chemistry deals with gases, metals, salts, metal ions, ect.

Organometallic Chemistry: Bioinorganic Chemistry:

Chapter 1 ⎯ Simple Bonding Theory (brief overview)

Solid State Chemistry Æ CBC951

Chapter 10 ⎯ Bioinorganic Chemistry

Chapter 1 ⎯ Symmetry and Group Theory

Chapter 3 ⎯ Coordination Chemistry - Structures and Isomers

Chapter 7 ⎯ Bioinorganic Chemistry (maybe)

Weight of final mark.

⎯⎯ Mid-term (~week 8 or 9) 30%

⎯⎯ Final exam 60%

Chapter 1 ⎯ Symmetry and Group Theory

Chapter 3 ⎯ Molecular Orbitals

Symmetry The operation performed on an object which leaves it

Symmetry Geometric entities that are used to manipulate

Point Symmetry The symmetry possessed by a single object that

Space Symmetry The symmetry describing the relationship of different

C2 axis is the symmetry element (no movement is involved)

Identity Î E Identity operation.

This operator leaves the object unchanged.

All molecules possess this symmetry element.

n-fold axis of symmetry Î Cn Rotation operation.

After rotation of 360°/n, the object returns to its original configuration.

Principal axis, or highest order

Plane of symmetry Î σv, σh, or σd reflection operation.

σv means vertical plane σh means horizontal plane σd means dihedral plane

σv means vertical plane σd means dihedral plane

Center of symmetry Î i Inversion operation.

Center of symmetry Î i Inversion operation.

Successive symmetry operation:

C32 = C3 × C3; C33 = C3 × C3 × C3

C32 is a symmetry operation, but not a symmetry element.

Improper axis of symmetry Î Sn Rotation-reflection operation

CF4/CH4/SiH4 Staggered form of C2H6

Schoenflies Notation vs Hermann Mauguin Notation

A chiral molecule does not have an improper rotation axis, Sn

A chiral molecule does not have an improper rotation axis, Sn

A chiral molecule does not have an improper rotation axis, Sn

A chiral molecule does not have an improper rotation axis, Sn

A chiral molecule does not have an improper rotation axis, Sn

A chiral molecule does not have an improper rotation axis, Sn

Chapter 1 ⎯ Symmetry and Group Theory

Chapter 3 ⎯ Molecular Orbitals

Symmetry Group ⎯ all the symmetry elements that describe a molecule.

Six C2 axes perpendicular to C6 39

There are infinitely many 3D point groups, however, in crystallography the

(a) The groups C1, Ci, Cs

C1 point group Cs point group

(b) The groups Cn, Cnv, and Cnh

(c) The groups Dn, Dnh, and Dnd

D6 point group D6h point group