Advance Inorganic

CHEM 521 - Advanced Inorganic Chemistry I
&
CHEM 721 - Selected Topics in Inorganic Chemistry
Fall 2021
Lecture 05, Tuesday, Sept 21, 2021
Dr. Ghayoor Abbas Chotana
Department of Chemistry and Chemical Engineering

SBA School of Science and Engineering
LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Quiz # 1
Quiz 1
Additional Notes Dr. Ghayoor Abbas

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
 Molecular Symmetry
 Identity, Rotation axis of symmetry, Plane of Symmetry, Inversion Center
 Improper Rotation (Examples, Number of unique operations)

 ReClassification of symmetry elements in Two major classes.
E = C1 E (C1) and Cn can be Grouped
Cn together as proper rotations
σ = S1
σ, i, and Sn can be Grouped
i = S2
together as Improper rotations
Sn
 Application of symmetry in predicting optical activity.

A molecule will be optically inactive if it will contain any of the
improper rotations i.e. σ, i, or Sn.
 Affect of presence/absence of proper rotations on optical activity
A molecule may be optically active even if it has
proper rotation Cn.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Improper Rotation (Number of unique operations)
 List the symmetry operations in various molecules
 See that each molecule has equal number of total proper
rotations and total improper rotations. i.e. if a molecule has
total 2n symmetry operations, half of these (n) will be proper
rotations and other half (n) will be improper rotation.
 Group together molecules of same symmetry in Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Improper Rotation
The Sn operation is rotation by 1/n of a
turn, followed by reflection in a plane
perpendicular to the axis
, e.g. ethane in the staggered conformation has an S6 axis because it

is brought to an indistinguishable arrangement by a rotation of 1/6 of a
turn, followed by reflection:
N.B. Neither C6 nor σh are present on their own in Ethane Staggered.

Chapter 1: Alan Vincent Dr. Ghayoor Abbas
Improper Rotation
 How many operations are generated by the symmetry element S6 in
staggered ethane?
 S61  S62  S63

 S64  S65  S66
 Which of these operations are unique?
 S61 = Unique  S62 = C31  S63 = i

 S64 = C32  S65 = Unique  S66 = E
 So S6 symmetry element only generate two unique operations i.e.
S61 and S65.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Improper Rotation
 Identify the improper rotation present in eclipsed ethane? Ans = S3
 How many unique operations are generated by the
symmetry element S3 in eclipsed ethane?
We can use the model a fiat equilateral triangle with one vertex “labelled”;
this label is only to help us to follow the effect of the operations, for
example the application of S3 moves the label as shown:
 Which of these operations are unique?

 S31 = Unique  S32 = C32  S33 = σh
 S34 = C31  S35 = Unique  S36 = E
 So S3 symmetry element only generate two unique operations i.e.
S31 and S35.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Symmetry Operations in a given Molecule
List all the (Unique) symmetry operations in Ammonia?
Ans:
E
2 C3 (C31 and C32)
3 σv
Total six operations.
Half i.e. 3 proper rotations (C31 and C32 + E=C33).

And remaining half i.e. 3 improper rotations (3 σv = 3 S1)
 Any molecule will generally have EVEN number of total
symmetry operations.
 Half of these will be proper rotations + identity E. And
remaining half will be improper rotations (Sn, all σ, i)
CHEM 521 &
CHEM 721
Inorganic
Chemistry
List all the (Unique) symmetry operations in [PtCl4]2?
Ans:
Proper rotations: E, 2C4 (C41 and C43) and colinear C2, 2C2’ , and 2C2’’
Improper rotations: i, 2S4 (S41 and S43), σh, 2σv, 2σd
Total sixteen operations.
Half i.e. 8 proper rotations. And half i.e. 8 improper rotations

 Half of these will be proper rotations + identity E. And
remaining half will be improper rotations (Sn, all σ, i)
CHEM 221/
Phy 335
Molecular
Symmetry
List all the (Unique) symmetry operations in Benzene?

Ans:
E 2C6 (C61 & C62) 2C3 (C31 & C32) C2 3C2’ 3C2”
Total Number of proper rotations = 12
Hence total improper rotations should also be 12
(And total symmetry operations be = 24)
σh 3σv 3σd i 2S3 (S31 & S35) 2S6 (S61 & S65)
Total 24 operations.
 Half of these will be proper rotations. And remaining half
will be improper rotations
CHEM 221/
Phy 335
Molecular
Symmetry
Which is more symmetrical, Tetrahedron or Octahedron?

CHEM 221/
Phy 335
Molecular
Symmetry
Symmetry Operations in Methane – CH4
List all the (unique) symmetry operations in CH4?
Ans: E S 4, C 2
What is the principal rotation axis in CH4? C3
How many unique operations are
generated by the C3 symmetry element? Two (C31+C32)
How many C3 axis are there in CH4? Four axis
So the number of unique operations
generated by four C3 axis in CH4 are ? 8C3 ( 4 pairs of C31 & C32)
Is there any other rotation axis in CH4 (besides C3)? Yes, C2
How many C2 rotation axis are there in CH4? Three axis
So the total number of proper rotations = 12
List all these. E 8C3 3C2
CHEM 221/
Phy 335
Molecular
Symmetry
Total number of proper rotations = 12 E 8C3 3C2
List the improper rotations in CH4?
Inversion center is absent.
How many planes are there in CH4? Six σd
Is there any improper rotation Sn axis in CH4? Yes, S4
How many unique operations are generated
by the S4 symmetry element? Three (S41 & S43
How many S4 rotation axis are there in CH4? Three
So the number of unique improper rotations
generated by three S4 axis in CH4 are ? 6 S4 (3 pairs of S41 & S43)
So the total number of symmetry operations = 24
List all these. E 8 C3 3 C2 6 σd 6 S4
CHEM 221/
Phy 335
Molecular
Symmetry
Symmetry Operations in Octahedron
List all the (Unique) symmetry operations in octahedron?
E
6 C4 (Three C4 axis, each having
two unique operations)
3 C2 (This C2 is co-linear with C4 principal axis)

6 C2 (This C2 passes through the middle of two
opposite edges. Since there are 12 edges in
octahedron, hence there are 6 such C2 axis) S4, C4, C2
8 C3 (This C3 passes through the middle of two C2

S6, C3
opposite faces. Since there are 8 faces in

octahedron, hence there are 4 such C3 axis,
each having two unique operations)
Total proper rotations = 24
(And total symmetry operations will be = 48)
CHEM 221/
Phy 335
Molecular
Symmetry
E 6 C4 3 C2 6 C2 8 C3
Total improper rotations should also be 24
i present S4, C4, C2
S6, C3
3 σh
6 σd
6 S4 (3 axis x 2)
8 S6 (4 axis x 2)
&
Fall 2021
Lecture 06, Thursday, Sept 23, 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
 Molecular Symmetry
 Identity, Rotation axis of symmetry, Plane of Symmetry, Inversion Center
 Improper Rotation (Examples, Number of unique operations in

Ethane eclipsed and staggered)
 Re-classification of symmetry elements in Two major classes.
E = C1 E (C1) and Cn can be Grouped together as proper rotations
Cn
σ = S1
σ, i, and Sn can be Grouped together as Improper rotations
i = S2
Sn
 Any molecule will generally have EVEN number of total symmetry
operations.
 Half of these will be proper rotations + identity E. And remaining half will
be improper rotations (Sn, all σ, i)
Sum of all proper rotation operation + Identity Operation = Sum of improper rotation operations + Sum of Planes + i

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 List the symmetry operations in various molecules.
 See that each molecule has equal number of total proper
rotations and total improper rotations. i.e. if a molecule has
total 2n symmetry operations, half of these (n) will be proper
rotations and other half (n) will be improper rotation.
 Group together molecules of same symmetry in Point Groups

 Combining two or more symmetry operations.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
List all the (Unique) symmetry operations in Benzene?

Ans:
E 2C6 (C61 & C62) 2C3 (C31 & C32) C2 3C2’ 3C2”
Total Number of proper rotation opertaions + Identity = 12
(And total symmetry operations be = 24)
σh 3σv 3σd i 2S3 (S31 & S35) 2S6 (S61 & S65)
 Any molecule will generally have EVEN number of total symmetry
operations.
 Half of these will be proper rotations + identity E. And remaining half
will be improper rotations (Sn, all σ, i)

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Which is more symmetrical, Tetrahedron or Octahedron or Cube?

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Start with identity E S 4, C 2
What is the principal rotation axis in CH4? C3
How many unique operations are
generated by the C3 symmetry element? Two (C31+C32)
How many C3 axis are there in CH4? Four axis
So the number of unique operations
generated by four C3 axis in CH4 are ? 8C3 ( 4 pairs of C31 & C32)
Is there any other rotation axis in CH4 (besides C3)? Yes, C2
How many C2 rotation axis are there in CH4? Three axis
So the total number of proper rotations + identity = 12
List all these. E 8C3 3C2
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Total number of proper rotations + E = 12 E 8C3 3C2
List the improper rotations in CH4?
Inversion center is absent.
How many planes are there in CH4? Six σd
Is there any improper rotation Sn axis in CH4? Yes, S4
How many unique operations are generated
by the S4 symmetry element? Two (S41 & S43)
How many S4 rotation axis are there in CH4? Three
So the number of unique improper rotations
generated by three S4 axis in CH4 are ? 6 S4 (3 pairs of S41 & S43)
So the total number of symmetry operations = 24
List all these. E 8 C3 3 C2 6 σd 6 S4
CHEM 521 &
CHEM 721
Inorganic
Chemistry
E
6 C4 (Three C4 axis, each having
two unique operations)
3 C2 (This C2 is co-linear with C4 principal axis)

6 C2 (This C2 passes through the middle of two
opposite edges. Since there are 12 edges in
octahedron, hence there are 6 such C2 axis) S4, C4, C2
8 C3 (This C3 passes through the middle of two C2

S6, C3
opposite faces. Since there are 8 faces in

octahedron, hence there are 4 such C3 axis,
each having two unique operations)
Total proper rotations + E = 24
(And total symmetry operations will be = 48)
CHEM 521 &
CHEM 721
Inorganic
Chemistry
E 6 C4 3 C2 6 C2 8 C3
Total improper rotations should also be 24
i present S4, C4, C2
S6, C3
3 σh
6 σd
6 S4 (3 axis x 2)
8 S6 (4 axis x 2)
CHEM 521 &
CHEM 721
Inorganic Symmetry elements in various Molecules
Chemistry
 Water H2O
E
C2
σ
σ' Different Molecules having
Same symmetry
 Pyridine
E
C2
σ
σ'
 Maleic acid or Phthalic acid
E
C2
σ
σ'
Chapter 1: Alan Vincent and Chapter 6: Shriver Dr. Ghayoor Abbas
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
 Symmetry operations in Water.
E, C2, σ, σ'
Point Group = C2v

 Symmetry operations in 1,2-Di-Chlorobenzene.
E, C2, σ, σ' Point Group = C2v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
 To assign point group, not necessary to list all the symmetry
operations. Only required to note the important/salient ones.
 Cn + n C2  Cn + σh = Dnh
For example benzene C6 + 6 C2  C6 + σh = D6h
What will be the point group of square? D4h
What will be the point group of equilateral triangle? D3h
 Cn + n C2  Cn + σv = Dnd
For example Ethane Staggered C3 + 3 C2  C3 + σv = D3d
 Cn + n C2  Cn + No σ = Dn
For example Ethane other conformation, C3 + 3 C2  C3 = D3
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
 Cn + σh = Cnh
For example Trans Ethene C2 + σh = C2h
 Cn + σv = Cnv
For example water C2 + σv = C2v
 Cn + No σ = Cn
For example hydrogen peroxide (H2O2), C2 + No σ = C2

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Low Symmetry Point Groups
 C1 + σ = Cs
 C1 + i = Ci
 C1
For example CHFClBr

CHEM 521 &
CHEM 721
Inorganic
Chemistry
High Symmetry Point Groups
 Td
 Oh
 Ih

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 Linear molecules are also of high symmetry (have C∞ + ∞ σ)
 In linear molecules, look for the presence or absence of inversion
center.
 C∞ + ∞ σ + i = D∞h
i.e. Linear molecule + inversion center present = D∞h
For example H2, N2 etc.
 C∞ + ∞ σ + No i = C∞v
i.e. Linear molecule + inversion center absent = C∞v
For example HCl, HCN etc.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Systematic Classification of Molecules

into Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

&
Fall 2021
Lecture 07, Tuesday, Sept 28, 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
Molecular Symmetry
 Group together molecules of same symmetry in Point
Groups.
Criteria
1. Cn axis: Higher rotation axis, greater symmetry.
2. Look for nC2  to principal Cn axis, if present, D symbol of
point groups
If nC2  to Cn axis absent, then C category of Point Groups.
3. Priority of planes
σh  σv  No σ

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Continue Grouping together molecules of same symmetry in
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
 To assign point group, not necessary to list all the symmetry
operations. Only required to note the important/salient ones.
 Cn + n C2  Cn + σh = Dnh
For example benzene C6 + 6 C2  C6 + σh = D6h
What will be the point group of square? D4h
What will be the point group of equilateral triangle? D3h
 Cn + n C2  Cn + σv = Dnd
For example Ethane Staggered C3 + 3 C2  C3 + σv = D3d
 Cn + n C2  Cn + No σ = Dn
For example Ethane other conformation, C3 + 3 C2  C3 = D3
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
 Cn + σh = Cnh
For example Trans Ethene C2 + σh = C2h
 Cn + σv = Cnv
For example water C2 + σv = C2v
 Cn + No σ = Cn
For example hydrogen peroxide (H2O2), C2 + No σ = C2

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Low Symmetry Point Groups
 C1 + σ = Cs
 C1 + i = Ci
 C1
For example CHFClBr

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 Td
 Oh
 Ih

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 Linear molecules are also of high symmetry (have C∞ + ∞ σ)
 In linear molecules, look for the presence or absence of inversion
center.
 C∞ + ∞ σ + i = D∞h
i.e. Linear molecule + inversion center present = D∞h
For example H2, N2 etc.
 C∞ + ∞ σ + No i = C∞v
i.e. Linear molecule + inversion center absent = C∞v
For example HCl, HCN etc.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

into Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Special group (i.e. high symmetry) absent.

Principal axis is C3 (hence groups of low symmetry not
applicable).
S6 absent.
3C2 perpendicular to C3 absent (hence C set of point groups)
σh absent
σv presnt
Point group = C3v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
PCl5
Principal axis is C3 (hence groups of low

symmetry not applicable).
S6 absent.
3C2 perpendicular to C3 Present

(hence D set of point groups)
σh Present
Point group = D3h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Trigonal bipyramidal variations
Point group Point group Point group Point group

= C2v = C2v = D∞h = D3h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

applicable).
S8 absent.
σh absent
σv present
Point group = C4v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

applicable).
S8 absent.
σh absent
σv present
Point group = C4v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Point group = C4v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

applicable).
S4 absent.
σh absent
σv present
Point group = C2v
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

applicable).
S8 absent.
4C2 perpendicular to C4 present (hence D set of point groups)
σh present
Point group = D4h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
C2v
D4h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

S6 absent.
3C2 perpendicular to C2 absent (hence C set of
point groups)
σh absent
σv present
Point group = C3v
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

applicable).
S4 absent.
σh absent
σv present
Point group = C2v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
[Co(en)3] ion
S6 absent.
(D set of point groups)
σh absent
σv absent
Point group = D3
Is [Co(en)3] ion Optically active?
Yes, since it only has C3 and 3 C2 i.e. No improper rotation
Hence this molecule will have two non superimposable enantiomers.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Special group (i.e. high symmetry) absent. [Co(en)2Cl2] ion
S4 absent.
2C2 perpendicular to C2 Absent (hence C set
of point groups)
σh absent
σv abssent
Point group = C2
Is [Co(en)2Cl2] ion Optically active?
Yes, since it only has C2
i.e. No improper rotation
Hence this molecule will have two non superimposable enantiomers.
&
Fall 2021
Lecture 08, Thursday, Sept 30, 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
Molecular Symmetry
 Group together molecules of same symmetry in Point
Groups.
Criteria
1. Cn axis: Higher rotation axis, greater symmetry.
2. Look for nC2  to principal Cn axis, if present, D symbol of
point groups
If nC2  to Cn axis absent, then C category of Point Groups.
3. Priority of planes
σh  σv  No σ

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

into Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Continue Grouping together molecules of same symmetry in
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
For aromatics, make sure to consider resonance Point Group
D2h
D6h
D2h
D6h D2h D4h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Point Groups with improper rotation

S4 Present
No other symmetry
elements is present.
Point group = S4
Only even number

Sn i.e. S4, S6, S8 etc.
Co(Cp)4 cluster
Tetramethylcyclooctatetraene
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Front View Side View

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Ethane Eclipsed

S6 absent.

σh Present
Point group = D3h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Ethane Staggered
S6 Present, however other symmetry
elements such as sigma also present.
σh absent
σv Present
Point group = D3d
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Point group = D3h
Point group = D3d
Point group for any other conformation = D3

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Cr(C6H6)2
S12 co-linear with C6 absent.
6C2 perpendicular to C2 present (hence D
set of point groups)
σh Present
Point group = D6h
Is this molecule chiral?
No, since it has planes as well as inversion center
Eclipsed = Dnh, Staggered = Dnd, any other Dn
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Ferrocene
Eclipsed Staggered
D5h D5d
Point group for any other conformation = D5

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Cyclohexane – Conformations

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Cyclohexane – Chair Conformation
Special group (i.e. high symmetry)

absent.
S6 Present.
3C2 perpendicular to C3 present (hence D
σh absent
σv present
Point group = D3d

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Cyclohexane – Boat Conformation

absent.
S4 Absent.
2C2 perpendicular to C2 Absent (hence C
σh absent
σv present
Point group = C2v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Diborane – B2H6

absent.
S4 Absent
2C2 perpendicular to C2 Present (hence D
σh Present
Point group = D2h

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Allene
S4 Present. But other symmetry elements also
present
2C2 perpendicular to C2 Present (hence D set
of point groups)
σh absent
σv present
Point group = D2d

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
1,3-Di substituted Allene

absent.
S4 co-linear with C2 Absent.
2C2 perpendicular to C2 Absent (hence C
σh absent Is this Optically active?
σv absent Yes, as there is no
Point group = C2 improper rotation
present
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
1,3-di substituted Allene
Point group = C2
Mirror image
non superimposable
It is not necessary to have four

different atoms on sp3 hybridized
carbon to have chirality.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Chirality & Point Groups
A chiral object is not superimposable on its mirror image.
Having four different substituents on carbon does not always result
in a chiral compound e.g. Tartaric acid.
Chiral compounds may have some symmetry in

themselves e.g. di-substituted allene has C2 axis.
First application of Molecular Symmetry S4
• An object is achiral if it has any of the Improper rotations

F
a. Plane σ b. Inversion center i c. Sn F

F

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups
Td
Oh

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Groups

&
Fall 2021
Lecture 09, Tuesday, Oct 05, 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
 Molecular Symmetry: Assignment of Point Groups to various molecules.
 Optical activity depends on the presence or absence of improper

rotations (sigma plane, inversion enter, and higher order improper
rotations).

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Chiral Point Groups
For a molecule to be optically active it must not contain any of
the improper rotations i.e. a. Plane σ b. Inversion center i c. Sn
 Hence, the molecules belonging to the following point group
can be optically active. C1, Cn, and Dn
(The rotational cubic groups T, O, and I can also be added in the list, but no
molecule with these symmetries are likely to be encountered)
 In these point groups only rotations are present, and none of
the improper rotations are present. (remember while counting).
 What is the point group of hydrogen peroxide? C2
 Is hydrogen peroxide optically active? NO, Why
 Free rotation about the OO bond continuously converts
the two hypothetical enantiomers.
 Here, Stereochemical non-rigidity precludes chirality.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Multiplications of two symmetry operations (is equal to a
single symmetry operation already present in the group).
 Properties of Point Groups
 Character Tables

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Combining Symmetry Operations
The product of two symmetry operations is a single operation
which is also present in the point group.
 If two symmetry operations 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:
σC2 = σ′
 This equation means that the operation C2 followed by the operation

σ gives the same result as the operation σ′.
 Note that the order in which the operations are performed is from
right to left.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 The product of two symmetry operations is a single
operation which is also present in the point group.
If two symmetry operations 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: σC = σ′
2
Confirm that this relationship is in fact true for the water

molecule. It may help to put a small label on your model to
show the effect of applying the operations:
Draw the position of the arrow after applying C2, and then after
applying σ to the result. Hence confirm that σC2 = σ′.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
What is the effect of reversing the order of the operations? i.e.
what is the product C2σ (σ followed by C2)?
• In this case the two operations COMMUTE i.e., σC2 = C2σ, but this is not
always true.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Use this diagram with an arrow to set up a complete multiplication table

for the symmetry OPERATIONS of the water molecule, putting the
product of the top operation, then the side operation, in the spaces:

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Use this diagram with an arrow to set up a complete multiplication table

for the symmetry OPERATIONS of the water molecule, putting the
product of the top operation, then the side operation, in the spaces:

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Inverse of Symmetry Operations
 A symmetry operation A can have inverse A‒1 if AA‒1 = E.
 In C2v point group

the inverse of C2 is C2 as C2C2 = E
Similarly
inverse of σv is σv as σv σv = E σv.
• Example H2O
Point group C2v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Group
 In math (group theory) the term “Group” has precise meaning.
 To qualify for being a group of ‘Group Theory’ one must
possess certain properties (four requirements).
1. The product of two members, and the square of any member is also a
member of the group. (Closure)
2. There must be an identity element. (Identity)
3. Combinations must be associative i.e. A(BC) = (AB)C
(Associativity)
4. Every member must have an inverse which is also a member of the
group. i.e. AA‒1 = E, if A is a member, A‒1 must also be the member.
(Inverse element)
• Example H2O belongs to Point group C2v
consist of symmetry operations E, C2, σ, σ`
To check if this group fulfils the conditions of being
a group of group theory, use multiplication table.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Group
 NH3
 Point group: C3v
• The product of two members, and the square
of any member is also a member of the group.
• There must be an identity
element.
• Combinations must be associative
i.e. A(BC) = (AB)C
• Every member must have an
inverse which is also a member of
the group. i.e. AA‒1 = E, if A is a
member, A‒1 must also be the
member. Note: anti-clockwise rotation
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Group
 Trihydroxy benzene,
 C3h
• The product of two members,
and the square of any member is
also a member of the group.
C3h E C3 C32 S3 S35 σh
element. E E C3 C32 S3 S35 σh
• Combinations must be C3 C3 C32 E S35 σh S3
associative i.e. A(BC) = (AB)C
C32 C32 E C3 σh S3 S35
inverse which is also a member S3 S3 S35 σh C32 E C3
of the group. i.e. AA‒1 = E, if A is S 5 S 5 σ S E C C 2
3 3 h 3 3 3
a member, A‒1 must also be the
member. σh σh S3 S35 C3 C32 E
 All the point groups (of molecular symmetry) are legitimate groups as
all of these fulfill the conditions of being a group of group theory.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Abelian Group
 In abstract algebra, an abelian group, also called a commutative
group, is a group in which the result of applying the group
operation to two group elements does not depend on the order in
which they are written.
 That is, these are the groups that obey the axiom of commutativity.
i.e. For all a, b in A, a • b = b • a.
• Example H2O
• σ v C2 = σ v `
• C2 σ v = σ v `
Hence C2v point group is an Abelian Group

i.e. AB = BA
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Abelian Point Group
 NH3
 C3v
σvC3 = σv``
C3 σ v = σ v `
So they do not commute hence
not an abelian group
A group in which the group

operation is not commutative is
called a "non-abelian group" or
"non-commutative group". Note: anti-clockwise rotation

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Classes of Symmetry Operations
 Can we group C3 & C32 together?

• Two operations A & B are in same class
if there is some operation X such that:
XAX–1 = B
Let us use σ to check C3 & C32
σv*C3*σv = ?
• σ*σv` = ?
• σσv = C32
Character table for C3v point group
• So we can group them together.
linear,
• Can we group all three sigma E 2C3 (z) 3σv
rotations
quadratic
together? A1 1 1 1 z x2+y2, z2
• So we list operations as E, 2C3, A2 1 1 -1 Rz

(x2-y2, xy) (xz,
3σv E 2 -1 0 (x, y) (Rx, Ry)
yz)

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 Point Group = C3h

 List all the operations of this point group.
• Generate multiplication table for C3h point
group.
E E C3 C32 S3 S35 σh
C3 C3 C32 E S35 σh S3
C32 C32 E C3 σh S3 S35
S3 S3 S35 σh C32 E C3
S35 S35 σh S3 E C3 C32
σh σh S3 S35 C3 C32 E

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 Can we group C3 & C3 together?
2
E E C3 C32 S3 S35 σh
C32 S35
 Can we group S3 & S35 together? C3 C3 E σh S3
C32 C32 E C3 σh S3 S35
• Two operations A & B are in S3 S3 S35 σh C32 E C3
same class if there is some S35 S35 σh S3 E C3 C32
operation X such that: XAX–1 = B σh σh S3 S35 C3 C32 E
• Let us use σ to check

Character table for C3h point group
C3 & C 3 2 e = exp(2πi/3)
• σC3σ = ? C3h E C3(z) (C3)2 σh S3 (S3)5
linear functions, quadratic
rotations functions
• σS3 = ? A' 1 1 1 1 1 1 Rz x2+y2, z2
1 e e* 1 e e* x+iy
• σS3 = C3 E'
1 e* e 1 e* e x-iy
(x2-y2, xy)
• So we cannot group A'' 1 1

1 e
1
e*
-1 -1 -1
-1 -e -e*
z
Rx+iRy
E'' (xz, yz)
them together. 1 e* e -1 -e* -e Rx-iRy

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Quiz 2

&
Fall 2021
Lecture 10, Thursday, Oct 07, 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
 Multiplications (or combining) of two symmetry operations (is equal to a single symmetry
operation already present in the group). e.g. in C2v group (water) σC2 = σ′ Note the order
 A symmetry operation A can have inverse A‒1 if AA‒1 = E. All the Point groups (of
molecular symmetry
Properties of Groups of Group Theory (Closure, Identity, inverse, associative) consisting of symmetry
1. The product of two members, and the square of any member is also a operations) are legitimate
member of the group. (Closure) groups as all of these
2. There must be an identity element. (Identity) fulfill the conditions of
being a group of group
3. Combinations must be associative i.e. A(BC) = (AB)C (Associativity)
theory.
4. Every member must have an inverse which is also a member of the
Abelian group, also called
group. i.e. AA‒1 = E, if A is a member, A‒1 must also be the
a commutative group, For
member.(Inverse element)
all a, b in A, a • b = b • a.
• Two operations A & B are in same class if there Character table for C3h point group. e = exp(2πi/3)
is some operation X such that: XAX–1 = B C E C (z) (C )2 σ S (S )5
3h 3 3 h 3 3
rotations functions
A' 1 1 1 1 1 1 Rz x2+y2, z2
linear,
C3v E 2C3 (z) 3σv quadratic 1 e e* 1 e e* x+iy
rotations E' (x2-y2, xy)
1 e* e 1 e* e x-iy
A1 1 1 1 z x2+y2, z2
A'' 1 1 1 -1 -1 -1 z
A2 1 1 -1 Rz
1 e e* -1 -e -e* Rx+iRy
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) E'' (xz, yz)
1 e* e -1 -e* -e Rx-iRy
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Point Group
 Trihydroxy benzene,
 C3h
• The product of two members,
and the square of any member is
also a member of the group.
element. E E C3 C32 S3 S35 σh
• Combinations must be C3 C3 C32 E S35 σh S3
associative i.e. A(BC) = (AB)C
C32 C32 E C3 σh S3 S35
inverse which is also a member S3 S3 S35 σh C32 E C3
of the group. i.e. AA‒1 = E, if A is S 5 S 5 σ S E C C 2
3 3 h 3 3 3
a member, A‒1 must also be the
member. σh σh S3 S35 C3 C32 E
 All the point groups (of molecular symmetry) are legitimate groups as
all of these fulfill the conditions of being a group of group theory.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Character Tables.
 Properties of Characters of Irreducible Representations in
Point Groups
 Labels for Irreducible Representations
 Non-Degenerate Representations

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Character Tables
The complete list of all the symmetry operations of a point group can be found in
tables called character table.
Each number is called a Character (which is essentially character/trace of a
matrix)
Character table for D2h point group Character table for D3h point group
linear, linear,
C C C σ σ σ quadrati D3h E 2C3 3C'2 σh 2S3 3σv quadratic
D2h E (z)2 (y)2 (x)2 i (xy) (xz) (yz)
rotation
c rotations
s A'1 1 1 1 1 1 1 x2+y2, z2
Ag 1 1 1 1 1 1 1 1 x2, y2, z2 A'2 1 1 -1 1 1 -1 Rz
B1g 1 1 -1 -1 1 1 -1 -1 Rz xy E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
B2g 1 -1 1 -1 1 -1 1 -1 Ry xz A''1 1 1 1 -1 -1 -1
B3g 1 -1 -1 1 1 -1 -1 1 Rx yz A''2 1 1 -1 -1 -1 1 z
Au 1 1 1 1 -1 -1 -1 -1 E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
B1u 1 1 -1 -1 -1 -1 1 1 z
B2u 1 -1 1 -1 -1 1 -1 1 y
B3u 1 -1 -1 1 -1 1 1 -1 x

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Character Tables
matrix)
e = exp(2πi/3)
C3h E C3(z) (C3)2 σh S3 (S3)5
rotations functions
Character table for C3v point group A' 1 1 1 1 1 1 Rz x2+y2, z2
linear, 1 e e* 1 e e* x+iy
E 2C3 (z) 3σv quadratic E' (x2-y2, xy)
rotations 1 e* e 1 e* e x-iy
A1 1 1 1 z x2+y2, z2 A'' 1 1 1 -1 -1 -1 z
A2 1 1 -1 Rz 1 e e* -1 -e -e* Rx+iRy
E'' (xz, yz)
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) 1 e* e -1 -e* -e Rx-iRy

CHEM 521 &
CHEM 721 Properties of Characters of Irreducible
Inorganic
Chemistry Representations in Point Groups
 Order (h) of the group
 The total number of symmetry operations in the group is called
the order ( h ).
 To determine the order of a group, simply total the number of
symmetry operation listed in the top row of the character table.
Character table for D3h point group
linear,
D3h E 2C3 3C'2 σh 2S3 3σv quadratic
Character table for C3v point group rotations
A'1 1 1 1 1 1 1 x2+y2, z2
linear, A'2 1 1 -1 1 1 -1 Rz
E 2C3 (z) 3σv quadratic
rotations E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
A1 1 1 1 z x2+y2, z2 A''1 1 1 1 -1 -1 -1
A2 1 1 -1 Rz A''2 1 1 -1 -1 -1 1 z
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
Order (h) = 6 Order (h) = 12

CHEM 521 &
Inorganic
 Classes of Symmetry Operations
 Symmetry operations are arranged in classes.
 All operations in a class have identical characters for their
transformation matrices and are grouped in the same column in
character tables.
 Two operations A & B are in same class if there is some operation X such that:
XAX–1 = B
Character table for C3v point group linear functions, quadratic
C3h E C3(z) (C3)2 σh S3 (S3)5
rotations functions
linear, A' 1 1 1 1 1 1 Rz x2+y2, z2
rotations
1 e e* 1 e e* x+iy
A1 1 1 1 z x2+y2, z2 E' (x2-y2, xy)
1 e* e 1 e* e x-iy
A2 1 1 -1 Rz A'' 1 1 1 -1 -1 -1 z
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) 1 e e* -1 -e -e* Rx+iRy
E'' (xz, yz)
1 e* e -1 -e* -e Rx-iRy
Number of Classes = 3
CHEM 521 &
Inorganic
 Each row of the character table is termed as irreducible
representations.
 The number of irreducible representations equals the number of
classes.
 This means that character tables have the same number of rows
and columns (they are square). Character table for D3h point group
Character table for C3v point group linear,
rotations
linear, A'1 1 1 1 1 1 1 x2+y2, z2
rotations
A'2 1 1 -1 1 1 -1 Rz
A1 1 1 1 Z x2+y2, z2
E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
A2 1 1 -1 Rz
A''1 1 1 1 -1 -1 -1
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz)
A''2 1 1 -1 -1 -1 1 z
Number of irreducible Rep = 3 E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
Number of Classes = 3 Number of irreducible Rep = 6

CHEM 521 &
Inorganic
 The character of an irreducible representation under identity
operation E is called its dimension.
 The sum of the squares of the dimensions (characters under E )
of each of the irreducible representations equals the order of the
group.
linear,
Character table for C3v point group D3h E 2C3 3C'2 σh 2S3 3σv quadratic
rotations
A'1 1 1 1 1 1 1 x2+y2, z2
linear, A'2 1 1 -1 1 1 -1 Rz
rotations
E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
A1 1 1 1 z x2+y2, z2
A''1 1 1 1 -1 -1 -1
A2 1 1 -1 Rz
A''2 1 1 -1 -1 -1 1 z
E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
12 + 12 + 22 = 6 12 + 12 + 22+ 12 + 12 + 22 = 12
CHEM 521 &
Inorganic
 For any irreducible representation, the sum of the squares of
the character multiplied by the number of operations in the
class, equals the order of the group.
Character table for C3v point group Character table for D3h point group
linear,
linear, D3h E 2C3 3C'2 σh 2S3 3σv quadratic
E 2C3 (z) 3σv quadratic rotations
rotations A'1 1 1 1 1 1 1 x2+y2, z2
A1 1 1 1 z x2+y2, z2 A'2 1 1 -1 1 1 -1 Rz
A2 1 1 -1 Rz E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) A''1 1 1 1 -1 -1 -1
A''2 1 1 -1 -1 -1 1 z
1*12 + 2*12 + 3*12 =6 E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
1*22 + 2*(-1)2 + 3(0)2 = 6 Order (h) = 12

CHEM 521 &
Inorganic
 Irreducible representations are orthogonal to each other.
 The sum of the products of the characters, multiplied together
for each class, for any pair of irreducible representations is 0.
Taking any pair of irreducible representations, multiplying together

the characters for each class, multiplying by the number of
operations in the class, and adding the products gives zero.

A1 and A2 are orthogonal
linear,
rotations 1*1*1 + 1*1*2 + (-1)1*3 = 0
A1 1 1 1 z x2+y2, z2
A2 1 1 -1 Rz A1 and E are orthogonal
1*2*1 + 1*(-1)2 + (1)(0)3 = 0
CHEM 521 &
Inorganic
 All groups include a totally symmetric representation, with
characters of 1 for all operations.

linear,
Character table for C3v point group rotations
A'1 1 1 1 1 1 1 x2+y2, z2
linear, A'2 1 1 -1 1 1 -1 Rz
rotations E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
A1 1 1 1 z x2+y2, z2 A''1 1 1 1 -1 -1 -1
A2 1 1 -1 Rz A''2 1 1 -1 -1 -1 1 z
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
Order (h) = 6 Order (h) = 12

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Labels for Irreducible Representations
Irreducible representations are assigned labels according to the following rules,
in which symmetric means a character of +1 and anti-symmetric means a
character of –1.
a. Letters (A, B, E, T) are assigned according to the dimension of the
irreducible representation (i.e. the character for the identity operation).
linear
functi
C2 2C'' quadratic
D4 E 2C4 (z) 2C'2 ons,
(z) 2 functions
rotati
ons
A1 1 1 1 1 1 x2+y2, z2
linear, A2 1 1 1 -1 -1 z, Rz
rotations B1 1 -1 1 1 -1 x2-y2
A1 1 1 1 z x2+y2, z2 B2 1 -1 1 -1 1 xy
A2 1 1 -1 Rz (x, y)
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) E 2 0 -2 0 0 (Rx, (xz, yz)
Ry)

CHEM 521 &
CHEM 721
Inorganic
Chemistry
a. Letters are assigned according to the dimension of the
irreducible representation (i.e. the character for the identity
operation)
3C2 linear,
E 8C3 6C2 6C4 i 6S4 8S6 3σh 6σd quadratic
=(C4)2 rotations
• Subscript g (gerade) A1g 1 1 1 1 1 1 1 1 1 1 x2+y2+z2

designates A2g 1 1 -1 -1 1 1 -1 1 1 -1
representations (2z2-x2-y2,
Eg 2 -1 0 0 2 2 0 -1 2 0
symmetric to inversion, x2-y2)
and T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)

• Subscript u (ungerade)
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
designates
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
representations A2u 1 1 -1 -1 1 -1 1 -1 -1 1
antisymmetric to Eu 2 -1 0 0 2 -2 0 1 -2 0
inversion T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Subscript 1 designates a representation symmetric to a C2 rotation
perpendicular to the principal axis.
and
subscript 2 designates a representation antisymmetric to the C2
rotation perpendicular to the principal axis.
linear
function quadratic
D4 E 2C4 (z) C2 (z) 2C'2 2C''2
s, functions
rotations
A1 1 1 1 1 1 x2+y2, z2
A2 1 1 1 -1 -1 z, Rz
B1 1 -1 1 1 -1 x2-y2
B2 1 -1 1 -1 1 xy
(x, y) (Rx,
E 2 0 -2 0 0 (xz, yz)
Ry)

CHEM 521 &
CHEM 721
Inorganic
Chemistry
If there are no perpendicular C2 axes, 1 designates a

representation symmetric to a vertical plane,
and
2 designates a representation antisymmetric to a vertical plane.
linear,
rotations
A1 1 1 1 z x2+y2, z2
A2 1 1 -1 Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Single primes are symmetric to sigma horizontal

and
double primes are antisymmetric to sigma horizontal
when a distinction between representations is needed e.g.

(C3h, C5h, D3h, D5h)
linear,
rotations
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
E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Non-Degenerate Representations
Character table for C2v point group Character table for ?? point group
C2 σv σv linear, 3C2 linear,

C2v E quadratic ?? E 8C3 6C2 6C4 i 6S4 8S6 3σh 6σd quadratic
(z) (xz) (yz) rotations =(C4)2 rotations
A1g 1 1 1 1 1 1 1 1 1 1 x2+y2+z2
A1 1 1 1 1 z x2, y2, z2
A2g 1 1 -1 -1 1 1 -1 1 1 -1
A2 1 1 -1 -1 Rz xy (2z2-x2-y2,
Eg 2 -1 0 0 2 2 0 -1 2 0
x2-y2)
B1 1 -1 1 -1 x, Ry xz
T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)
B2 1 -1 -1 1 y, Rx yz
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
What information is A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
available on the right
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
side of character table? T2u 3 0 1 -1 -1 -3 1 0 1 -1

CHEM 521 &
CHEM 721
Inorganic
Chemistry
 The C2v character table
is, in part:
Taking the C2 axis as the z axis, to what irreducible representations do s, px, py,
pz, dxy, dyz, dxz, dx2-y2, dz2 orbitals and rotations (Rx, Ry, Rz) belong in the C2v
symmetry?
Orbital Irreducible Orbital Irreducible Orbital Irreducible Rotati Irreducible
Representati Representati Representati on Representati
on on on on
s dxy px Rx
dz2 dyz py Ry
dx2-y2 dxz pz Rz
CHEM 521 &
CHEM 721
Inorganic
Chemistry
The C2v character table is, in part:
Let us look at the effect on a px orbital of a C2 rotation

about the z axis:
The sign of the px orbital is changed, so how can the Answer = 1
operation be represented, by +1 or –1? px becomes –px or: C2Px = –lPx
Let us look at the effect of various reflections on the px orbital —
consider first a reflection in the xz plane which passes through the orbital:
What does the orbital look like after applying the σ(xz) operation?
Just the same, because the plane passes through the middle of both lobes.
What number will represent the operation σ(xz)?
+1 i.e. σ(xz) px = lpx

CHEM 521 &
CHEM 721
Inorganic
Chemistry
What about the reflection in the yz plane
— what is the result of σ(yz)px, and
hence what number represents σ(yz)?
σ(yz)px = –px, hence σ(yz) is represented by –1:
What number represents the effect of the identity operation, E? +1

We have now looked at the numbers representing the four operations
E C2 σ(xz) σ(yz).
These four operations form a group, can you remember which one it is? C2v
We say that the four numbers form the B1 representation of
the C2v group:
We also say that x belongs to the B1 representation of C2v because this set of numbers
represents the effect of the group operations on a px orbital, or indeed anything with the
same symmetry properties as the x axis.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Find the effect of the group operations on a py

orbital, and hence derive a set of numbers which
represent the effect of the operations on py.
We say that y (or a py orbital) is SYMMETRIC to E and σ(yz) and

ANTISYMMETRIC to C2 and σ(xz) in C2v symmetry. The py orbital thus
belongs to the B2 representation:

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Find the representation of the C2v point group to

which a pz orbital belongs, and confirm that the
numbers multiply together in the same way as the
operations:
The pz orbital belongs to the TOTALLY SYMMETRIC or A1 representation of

the C2v point group, because the pz orbital is not changed by any of the group
operations.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
There is one further set of numbers called the A2 representation which fulfills the
two conditions given above for the C2v point group. The full set of representations
is included in a table called the CHARACTER TABLE of the group:
The numbers in this table should strictly be

called the CHARACTERS of the
IRREDUCIBLE REPRESENTATIONS of
the group. The meaning of this long title
will become apparent in time.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Let us now try a slightly more
complicated d orbitals.
To which of the four representations of C2v
does dxy belong?

CHEM 521 &
CHEM 721
Inorganic
Chemistry
It is also possible to find the representation to which other directional properties

belong, e.g. a rotation about the x axis. If you hold a pencil horizontally in front of
you and rotate it on its own axis (x), then, still rotating it, give it a half turn rotation
about a vertical axis, its direction of rotation about its own axis will appear to have
been reversed (try doing it!) Thus rotation about x is (symmetric/antisymmetric) to
C2. Antisymmetric.
You need a particularly twisted mind to assign
rotations to a symmetry class, and you may need to
ask someone to explain it to you if you are not
prepared to accept it. The information we have just
deduced is included in the full character table e.g.:
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Assignment of orbitals and rotations
C2h E C2 (z) i σh E C2 i σh
Ag 1 1 1 1 s 1 1 1 1 Ag
px
Bg 1 -1 1 -1
py
Au 1 1 -1 -1
pz
Bu 1 -1 -1 1 dxy
dyz
dzx
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py
Au 1 1 -1 -1
pz
Bu 1 -1 -1 1 dxy
dyz
dzx
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz
Bu 1 -1 -1 1 dxy
dyz
dzx
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy
dyz
dzx
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz
dzx
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx 1 −1 1 −1 Bg
dx2-y2
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx 1 −1 1 −1 Bg
dx2-y2 1 1 1 1 Ag
dz2
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx 1 −1 1 −1 Bg
dx2-y2 1 1 1 1 Ag
dz2 1 1 1 1 Ag
Rx
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx 1 −1 1 −1 Bg
dx2-y2 1 1 1 1 Ag
dz2 1 1 1 1 Ag
Rx 1 −1 1 −1 Bg
Ry
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx 1 −1 1 −1 Bg
dx2-y2 1 1 1 1 Ag
dz2 1 1 1 1 Ag
Rx 1 −1 1 −1 Bg
Ry 1 −1 1 −1 Bg
Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Ag 1 1 1 1 s 1 1 1 1 Ag
px 1 1 1 1 Bu
Bg 1 -1 1 -1
py 1 1 1 1 Bu
Au 1 1 -1 -1
pz 1 1 −1 −1 Au
Bu 1 -1 -1 1 dxy 1 1 1 1 Ag
dyz 1 −1 1 −1 Bg
dzx 1 −1 1 −1 Bg
dx2-y2 1 1 1 1 Ag
dz2 1 1 1 1 Ag
Rx 1 −1 1 −1 Bg
Ry 1 −1 1 −1 Bg
Rz 1 1 1 1 Ag

&
Fall 2021
Lecture 11, Tuesday, Oct 12, 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
 Multiplications (or combining) of two symmetry operations (is
equal to a single symmetry operation already present in the
group).
 Properties of Point Groups (Closure, Identity, inverse,
associative)
 Character Tables Character table for C3v point group
linear,
 Order (h) of the group, E 2C3 (z) 3σv
rotations
quadratic
A1 1 1 1 z x2+y2, z2
 Classes of operations A2 1 1 -1 Rz
 Irreducible representations
 Labels for irreducible representations
 Assigning various orbitals (s, p, or d) and rotations to various
irreducible representations.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Reducible Representations
 Reduction of reducible representations into irreducible
representations.
 Applications in Chemical Bonding
 Determination of orbitals suitable for hybridization for a giben
geometry
 Direct Products
 Matrix representation for operations

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Character Tables
matrix)
Character table for D2h point group Character table for D3h point group
linear, linear,
C C C σ σ σ quadrati D3h E 2C3 3C'2 σh 2S3 3σv quadratic
D2h E (z)2 (y)2 (x)2 i (xy) (xz) (yz)
rotation
c rotations
s A'1 1 1 1 1 1 1 x2+y2, z2
Ag 1 1 1 1 1 1 1 1 x2, y2, z2 A'2 1 1 -1 1 1 -1 Rz
B1g 1 1 -1 -1 1 1 -1 -1 Rz xy E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
B2g 1 -1 1 -1 1 -1 1 -1 Ry xz A''1 1 1 1 -1 -1 -1
B3g 1 -1 -1 1 1 -1 -1 1 Rx yz A''2 1 1 -1 -1 -1 1 z
Au 1 1 1 1 -1 -1 -1 -1 E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
B1u 1 1 -1 -1 -1 -1 1 1 z
B2u 1 -1 1 -1 -1 1 -1 1 y
B3u 1 -1 -1 1 -1 1 1 -1 x

CHEM 521 &
Inorganic
 Classes of Symmetry Operations
 Symmetry operations are arranged in classes.
 All operations in a class have identical characters for their
transformation matrices and are grouped in the same column in
character tables.
 Two operations A & B are in same class if there is some operation X such that:
XAX–1 = B
Character table for C3v point group linear functions, quadratic
C3h E C3(z) (C3)2 σh S3 (S3)5
rotations functions
linear, A' 1 1 1 1 1 1 Rz x2+y2, z2
rotations
1 e e* 1 e e* x+iy
A1 1 1 1 z x2+y2, z2 E' (x2-y2, xy)
1 e* e 1 e* e x-iy
A2 1 1 -1 Rz A'' 1 1 1 -1 -1 -1 z
E 2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy) (xz, yz) 1 e e* -1 -e -e* Rx+iRy
E'' (xz, yz)
1 e* e -1 -e* -e Rx-iRy
CHEM 521 &
Inorganic
 Each row of the character table is termed as irreducible
representations.
 The number of irreducible representations equals the number of
classes.
 This means that character tables have the same number of rows
and columns (they are square). Character table for D3h point group
Character table for C3v point group linear,
rotations
linear, A'1 1 1 1 1 1 1 x2+y2, z2
rotations
A'2 1 1 -1 1 1 -1 Rz
A1 1 1 1 Z x2+y2, z2
E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
A2 1 1 -1 Rz
A''1 1 1 1 -1 -1 -1
A''2 1 1 -1 -1 -1 1 z
Number of irreducible Rep = 3 E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
Number of Classes = 3 Number of irreducible Rep = 6

CHEM 521 &
CHEM 721
Inorganic
Chemistry
a. Letters are assigned according to the dimension of the
irreducible representation (i.e. the character for the identity
operation)
• Subscript g (gerade) E 8C3 6C2 6C4
3C2
i 6S4 8S6 3σh 6σd
linear,
quadratic
=(C4)2 rotations
designates representations
symmetric to inversion, A1g 1 1 1 1 1 1 1 1 1 1 x2+y2+z2
and A2g 1 1 -1 -1 1 1 -1 1 1 -1
• Subscript u (ungerade) (2z2-x2-y2,
Eg 2 -1 0 0 2 2 0 -1 2 0
designates representations x2-y2)
antisymmetric to T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)
inversion
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
Irreducible representations A1u 1 1 1 1 1 -1 -1 -1 -1 -1

Can further be categorized as A2u 1 1 -1 -1 1 -1 1 -1 -1 1
1. Degenerate representations and Eu 2 -1 0 0 2 -2 0 1 -2 0
2. Nondegenerate representations T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Reducible Representations
linear,
C2v E C2 (z) σv(xz) σv(yz) quadratic
rotations
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
1 1 1 1
2 2 0 0 A1 + A2 1 1 -1 -1
__________________
2 2 0 0
2 0 2 0 A1 + B1
3 1 -1 -3 2A2 + B1
30 0 0 10 ????????
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Reducing Reducible Representations
Group Theory solves real problems involves generating a reducible
representation, and then reducing it to its constituent irreducible
representations
REDUCTION FORMULA
Number of times an irreducible representation occurs in the
reducible representation
1
  R  I  N
h overallclasses
where h = order of the group (= number of operations in the group)
χR = character of the reducible representation
χI = character of the irreducible representation
N = number of symmetry operations in the class
CHEM 521 &
CHEM 721
Inorganic
Chemistry

30 0 0 10 linear,
rotations
# of times A1 = ¼[30*1*1+0*1*1+0*1*1+10*1*1] A1 1 1 1 1 z x 2 , y2 , z 2
# of times A1 = ¼[40] = 10 A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
# of times A2 = ¼[30*1*1+0*1*1+0*(-1)*1+10*(-1)*1] B2 1 -1 -1 1 y, Rx yz
# of times A2 = ¼[20] = 5
# of times B1 = ¼[30*1*1+0*(-1)*1+0*1*1+10*(-1)*1]
# of times B1 = ¼[20] = 5
30 0 0 10 =
# of times B2 = ¼[30*1*1+0*(-1)*1+0*(-1)*1+10*1*1] 10A1 + 5A2 + 5B1 + 10B2
# of times B2 = ¼[40] = 10

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Let us consider the representation of C3v (labelled Γ1)
Here N = 1 for E, 2 for rotations and 3 for reflections
We will use the character table for C3v point group for the reduction
Number of times an irreducible representation occurs in the reducible
representation
1
  R  I  N
h overallclasses
1 2C3 linear,
C3v E 3σv quadratic
No. of A1 [( 4
11)  (11 2)  (2 1 3)]  0 (z) rotations
6   
E C 3 σ v
A1 1 1 1 z x2+y2, z2
A2 1 1 -1 Rz
1
No. of A 2  [( 4
21)  (1 1 2)  (2  0  3)]  2 (x, y) (Rx, (x2-y2, xy) (xz,
6    E 2 -1 0
Ry) yz)
E C σ
3 v
1
No. of E  [( 4
21)  (1 1 2)  (2  0  3)]  1
6    Thus Γ1 reduces to 2A2+E
E C σ
3 v

CHEM 521 &
CHEM 721
Inorganic
Chemistry
linear,
rotations
A1 1 1 1 z x2+y2, z2
A2 1 1 -1 Rz

CHEM 521 &
CHEM 721
Inorganic
Chemistry
C2h E C2 (z) i σh
Ag 1 1 1 1
Bg 1 -1 1 -1
Au 1 1 -1 -1
Bu 1 -1 -1 1
linear,
C3v E 2C3 (z) 3σv quadratic
rotations
A1 1 1 1 z x2+y2, z2
A2 1 1 -1 Rz
linear,
rotations
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

CHEM 521 &
CHEM 721
Inorganic
Chemistry

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Direct Products
Direct product: The representation of the product of two
representations is given by the product of the characters of the two
representations.
B1.B2
The direct product of two irreducible representations will be a
new representation which is either an irreducible or a reducible
representations.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Direct Products
The direct product of two irreducible representations will be a new

representation which is either an irreducible or a reducible representations.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Direct Products Rules
1. If all the combined irreducible representations are nondegenerate,
then the product will be a nondegenerate representation too.
E 2C4 (z) C2 2σv 2σd linear,
E 2C4 (z) C2 2σv 2σd quadratic
B1 1 -1 1 1 -1 rotations
A1 1 1 1 1 1 z x2+y2, z2
B2 1 -1 1 -1 1
A2 1 1 1 -1 -1 Rz
A2 1 1 1 -1 -1 B1 1 -1 1 1 -1 x2-y2
2. The product of nondegenerate B2 1 -1 1 -1 1 xy
representation and a degenerate E 2 0 -2 0 0 (x, y) (Rx, Ry) (xz, yz)
representation is a degenerate Product table for C4v point group
representation A1 A2 B1 B2 E
E 2C4 (z) C2 2σv 2σd A1 A1 A2 B1 B2 E
B2 1 -1 1 -1 1 A2 A2 A1 B2 B1 E
B1 B1 B2 A1 A2 E
E 2 0 -2 0 0
B2 B2 B1 A2 A1 E
E 2 0 -2 0 0 E E E E E A1+A2+B1+B2
CHEM 521 &
CHEM 721
Inorganic
Chemistry
3. The direct product of any representation with the totally symmetric
representation is the representation itself.
Totally symmetric representation Character table for C4v point group
= A, A1, Ag, A1g, etc. linear,
rotations
E 2C4 (z) C2 2σv 2σd
A1 1 1 1 1 1 z x2+y2, z2
A1 1 1 1 1 1 A2 1 1 1 -1 -1 Rz
E 2 0 -2 0 0 B1 1 -1 1 1 -1 x2-y2
E 2 0 -2 0 0 B2 1 -1 1 -1 1 xy
E 2 0 -2 0 0 (x, y) (Rx, Ry) (xz, yz)
Product table for C4v point group

4. The direct product
E 2C4 (z) C2 2σv 2σd A1 A2 B1 B2 E
of degenerate
E 2 0 -2 0 0 A1 A1 A2 B1 B2 E
representations is a
A2 A2 A1 B2 B1 E
reducible E 2 0 -2 0 0
B1 B1 B2 A1 A2 E
representation 4 0 4 0 0
B2 B2 B1 A2 A1 E
Reduced to = A1 + A2 + B1 + B2 E E E E E A1+A2+B1+B2
CHEM 521 &
CHEM 721
Inorganic
Chemistry
5. The direct product of an irreducible representation with itself is or
contains the totally symmetric representation.
E 2C4 (z) C2 2σv 2σd Character table for C4v point group
A2 1 1 1 -1 -1 linear,
A2 1 1 1 -1 -1 rotations
A1 1 1 1 1 1 A1 1 1 1 1 1 z x2+y2, z2
A2 1 1 1 -1 -1 Rz
E 2C4 (z) C2 2σv 2σd B1 1 -1 1 1 -1 x2-y2
E 2 0 -2 0 0 Reduced to = B2 1 -1 1 -1 1 xy
A1 + A2 + B1 E 2 0 -2 0 0 (x, y) (Rx, Ry) (xz, yz)
E 2 0 -2 0 0
+ B2 Product table for C4v point group
4 0 4 0 0
A1 A2 B1 B2 E
6. Only the direct product A1 A1 A2 B1 B2 E
of representation with E 2C4 (z) C2 2σv 2σd A2 A2 A1 B2 B1 E
itself is or contains the A2 1 1 1 -1 -1 B1 B1 B2 A1 A2 E
totally symmetric B1 1 -1 1 1 -1 B2 B2 B1 A2 A1 E
representation. B2 1 -1 1 -1 1 E E E E E A1+A2+B1+B2
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Direct Products
The product of any
singly degenerate
representation with itself
is a totally symmetric
representation
The product of any

representation with the
totally symmetric
representation is totally
symmetric representation
Totally symmetric
representation =
A, A1, Ag, A1g, etc.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Direct Products
Direct product: The representation of the product of two
representations is given by the product of the characters of the two
representations.
Used to determine the:

 representation for a wave function
 ground and excited state symmetry
 allowedness of a reaction
 determining the symmetry of many electron states
 allowedness of a vibronic transition
 allowedness of a electronic transition

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Chemical Bonding
Hybridization
sp3 hybridization.
• Why sp3 hybridization results in tetrahedral geometry? and

dsp2 hybridization results in square planar geometry?
• Can tetrahedral geometry be achieved by any other hybridization?
• Which of the five d orbitals is used in dsp2 hybridization? (square planar case)
• Which of the five d orbitals is used in dsp3 hybridization? (trigonal bipyramidal)
• Which two d orbitals are used in d2sp3 hybridization? (octahedral case)
• What is the hybridization on square anti-prismatic geometry?
• What is the hybridization of central metal atom in MnO4̶ 1 and CrO42?
• Do d orbitals participate in bonding in SF6 and PF5? What is the
hybridization of central atom in SF6 (d2sp3 or sp?) and PF5?
Symmetry helps us to answer/understand all such questions
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Hybridization – Tetrahedral Geometry
Which set of orbitals is suitable for hybridization to generate
Tetrahedral shape (arrangement of bond pairs + lone pairs).
Point Group: Td
Basis Set: Four arrows pointing away central atom.
Td E 8C3 3C2 6S4 6σd
Reducible Rep: 4 1 0 0 2
Reduced to: A1+T2 Character table for Td point group
A1 = s linear,
E 8C 3C 6S 6σ rotation
quadrati
3 2 4 d
c
T2 = (px, py, pz) or (dxy,dyz, dzx) s
A 1 1 1 1 1 x +y +z 2 2 2
1
Two Possible combinations A 1 1 2 1 -1 -1
(2z -x - 2 2
s, px, py, pz i.e. sp3 as in CH4 E 2 -1 2 0 0
y , x -y ) 2 2 2
(R , R ,
s, dxy, dyz, dzx T 3 01 -1 1 -1
R)
x y
z
i.e. sd3 as in CrO42+ ion T 3 02 -1 -1 1 (x, y, z)

(xy, xz,
yz)

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Hybridization – Octahedral Geometry
Octahedral shape (hybrid orbitals to accommodate total six bond
pairs + lone pairs in ML6, BrF5, or XeF4 etc.). Basis Set: Six
Point Group: Oh arrows pointing
away central atom.
Reducible Rep: 6 0 0 2 2 0 0 Character 0 table4 for O 2point group h
linear,
Reduced to: A1g + Eg + T1u E 8C 6C 6C
3C
3 2 4
2
i 6S 8S 3σ 6σ rotation quadratic
2 4 6 h d
=(C ) 4
s
A1g = s A 1 1 1 1 1g1 1 1 1 1 1 x +y +z 2 2 2
Eg = dx2-y2, dz2 A 1 1 -1 -1 2g1 1 -1 1 1 -1

(2z -x - 2 2
E 2 -1 0 0 g 2 2 0 -1 2 0 2 2 2
y , x -y )
T1u = (px, py, pz) (R , R , x y
T 3 0 -1 1 1g-1 3 1 0 -1 -1
R)
One Possible combination (xz, yz,
z
T 3 0 1 -1 -1 3 -1 0 -1 1
2 2
s, px, py, pz , dx -y , dz 2 2g
xy)
A 1 1 1 1 1u1 -1 -1 -1 -1 -1
i.e. sp3d2 A 1 1 -1 -1
E 2 -1 0 0
2u
u
1
2
-1 1 -1 -1 1
-2 0 1 -2 0
T 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
Applicable to ML6 T 3 0 1 -1 -1
1u
2u -3 1 0 1 -1

CHEM 521 &
CHEM 721
Inorganic Hybridization – Trigonal Bipyramidal Geometry
Chemistry
What set of orbitals are suitable for hybridization to generate

trigonalbipyramidal shape.
Point Group: D3h
Basis Set: Five arrows pointing away central atom.
Reducible Rep: 5 2 1 3 0 3
Reduced to: 2A1`+ E` + A2``
A1` = s , dZ2 Character table for D3h point group
E` = (px, py) or (dxy, dx2-y2) D3h E 2C3 3C'2 σh 2S3 3σv

linear,
quadratic
rotations
A2`` = pz A'1 1 1 1 1 1 1 x2+y2, z2
A'2 1 1 -1 1 1 -1 Rz
Two Possible combinations E' 2 -1 0 2 -1 0 (x, y) (x2-y2, xy)
s, px, py, pz , dz2 i.e. sp3d A''1 1 1 1 -1 -1 -1
A''2 1 1 -1 -1 -1 1 z
s, pz, dxy, dx2-y2, dz2 i.e spd3 E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)

CHEM 521 &
CHEM 721
Inorganic Hybridization – Square Planar Geometry
Chemistry
What set of orbitals are suitable for hybridization to generate

square planar shape.
Basis Set: Four arrows
Point Group: D4h
pointing away central atom.
Reducible Rep: 4 0 0 2 0 0 0 4 2 0
Reduced to: A1g+ B1g + Eu linea
2C4 rs, quad
E C2 2C'2 2C''2 i 2S4 σh 2σv 2σd
A1g = s , dZ 2 (z) rotat ratic
ions
x2+y2
B1g = dx2-y2 A
1g1 1 1 1 1 1 1 1 1 1
, z2
A 1 1 1 -1 -1 1 1 1 -1 -1 Rz
Eu = (px, py) 2g
B
1g1 -1 1 1 -1 1 -1 1 1 -1 x2-y2
Two Possible combinations B 1 2g -1 1 -1 1 1 -1 1 -1 1

(Rx,
xy
(xz,
E
g 2 0 -2 0 0 2 0 -2 0 0
2 Ry) yz)
s, px, py, dx2-y2 i.e. sp d A
1u1 1 1 1 1 -1 -1 -1 -1 -1
px, py, dx2-y2, dz2 i.e. d2p2 A

2u
B
1
1
1
-1
1
1
-1
1
-1
-1
-1
-1
-1
1
-1
-1
1
-1
1
1
z
1u
B2u 1 -1 1 -1 1 -1 1 -1 1 -1
Eu 2 0 -2 0 0 -2 0 2 0 0 (x, y)

CHEM 521 &
CHEM 721
Inorganic Hybridization
Chemistry

CHEM 521 &
CHEM 721
Chemistry

CHEM 521 &
CHEM 721
Chemistry
Determine the set of orbitals which are suitable for hybridization to generate
the following geometries;
Terahedral
Octahedral
Square planar
Trigonal
Trigonal bipyramidal
Other possible geometries to practice
Trigonal pyramidal
Square Pyramidal
Trigonal Antiprismatic
Trigonal Prismatic
Square Prismatic
Square Antiprismatic
Tricapped trigonal prismatic
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrices
For those who are interested in knowing
• How to represent symmetry operations in the form of matrices,
and
• How to generate a reducible representation from matrices

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrices
A matrix is an ordered
array of numbers, such as
Matrix Multiplication: To multiply matrices, the number of vertical
columns of the first matrix must be equal to the number of horizontal
rows of the second matrix.
To find the product, add, term by term, the products of each row of the
first matrix by each column of the second (each term in a row must be
multiplied by its corresponding term in the appropriate column of the
second matrix). Place the resulting sum in the product matrix with the
row determined by the row of the first matrix and the column
determined by the column of the second matrix:.
Here,

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrices Multiplication
To multiply matrices, the number of vertical columns of the first
matrix must be equal to the number of horizontal rows of the second
matrix.
Here,
This example has two rows and two columns in each initial matrix, so
it has two rows and two columns in the product matrix.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
[(1)(1) + (2)(0) + (3)(0) (1)(0) + (2)(-1) + (3)(0) (1)(0) + (2)(0) + (3)(1)]i = [1 -2 3]i
Here, i = 1, j = 3, and k = 3, so the product matrix has one row (i) and
three columns (j).
Here i = 3, j = 1, and k = 3, so the product matrix has three rows ( i )

and one column (j).
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Exercise. Do the following multiplications:

CHEM 521 &
CHEM 721
Inorganic Symmetry Operations: Matrix Representations
Chemistry
We will now consider how the C2v point group symmetry

operations transform a set of x , y , and z coordinates.
Each symmetry operation can be expressed as a
transformation matrix as follows:
[New coordinates] = [transformation matrix] [old coordinates].
As examples, consider how transformation matrices can be used to
represent the symmetry operations of the C2v point group:
C2: Rotate a point having coordinates (x, y, z) about the C2(z) axis.
The new coordinates are given by.
Transformation matrix for C2.

CHEM 521 &
CHEM 721
Chemistry

C2: Rotate a point having coordinates (x, y, z) about
the C2(z) axis. The new coordinates are given by.
In matrix notation,

CHEM 521 &
CHEM 721
Chemistry
σxz: Reflect a point with coordinates (x, y, z)

through the xz plane.
Transformation matrix for σxz.
In matrix notation,

CHEM 521 &
CHEM 721
Chemistry
The transformation matrices for the four symmetry

operations of the group are
We call this a matrix representation of the C2v point group.

These matrices combine in the same way as the operations themselves.

CHEM 521 &
CHEM 721
Chemistry

operations of the C2v group are
The character, defined only for a square matrix, is the trace of the
matrix, or the sum of the numbers on the diagonal from upper left to
lower right.
For the C2v point group, the following characters are obtained from
the preceding matrices:

CHEM 521 &
CHEM 721
Chemistry
Consider the C3 rotation shown in Figure

Counterclockwise rotation of 120° results
in a new x’ and y’ as shown, which can be
described in terms of the vector sums of x
and y by using trigonometric functions:
The transformation matrices for the C3 symmetry operations is:

CHEM 521 &
CHEM 721
Chemistry
General case: x’ = x cos θ – y sin θ

y’ = x sin θ + y cos θ
For C3: θ = 2π/3 = 120°

General Transformation Matrix for proper
rotation (anti clockwise) by θ° about z axis:
Cn = Where θ = 2π/n
General Transformation Matrix

for improper rotation (anti Sn =
clockwise) by θ° about z axis:
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Vector Basis for Td
 All operations of Td simply interchange vectors,
so we may follow the effects of each operation by
noting the transformations of the vector tips, A, B,
C, and D.
 The character generated by any operation of a
class is the same as all other members of the class.
 We do not need to subject the set to all h = 24 operations of the
group Td , just one operation from each of the five classes of
operations: E, 8C3 , 3C2 , 6S4 , σd.
 We can describe the effect of each representative operation by a
4x4 transformation matrix that shows how A, B, C, and D are
interchanged.
 The traces of the matrices will give us the characters of reducible
representation.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrix for Operations

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Gathering all reducible characters from the trace of each matrix we find the
following:

&
Fall 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
1

Molecular Symmetry
 R  I  N
 Reducible Representations h overallclasses
 Reduction of reducible representations into irreducible
representations
 Direct Products
 Applications in Chemical Bonding
 Determination of orbitals suitable for hybridization for a
given geometry Td E 8C3 3C2 6S4 6σd
Reduced to: A1+T2
A1 = s and T2 = (px, py, pz) or (dxy,dyz, dzx) Two Possible combinations
s, px, py, pz i.e. sp3 as in CH4, and s, dxy, dyz, dzx i.e. sd3 as in CrO42+ ion
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Splitting of orbitals in various geometries/fields
 Matrix representation for symmetry operations.

CHEM 221/
Phy 335
Molecular
Splitting of Orbitals in a Given Symmetry (Point Group)
Symmetry
In atoms or ions, which have

spherical symmetry i.e. Point
Group Kh, all the five d orbitals
remain degenerate.

CHEM 221/
Phy 335
Molecular
Symmetry
In atoms or ions, which have spherical symmetry i.e. Point Group Kh, all the five
d orbitals remain degenerate.
How the five d orbitals split in octahedral field?
How the five d orbitals split in Tetrahedral field?
How the five d orbitals split in other (such as trigonal bipyramidal, square
planar, square pyramidal etc.) fields?
Notes Dr. Ghayoor Abbas
CHEM 221/
Phy 335
Molecular
Symmetry
 In atoms or ions, which have spherical symmetry i.e. Point Group Kh, all the
five d orbitals remain degenerate.
 However upon application of ligand field i.e. placing the metal ion in a field of
less symmetry such as octahedral or tetrahedral, removes this degeneracy.
 The d ( or p, f, g etc) orbitals are said to be split in given field e.g. in octahedral
field, the five d orbitals split in to three low energy orbitals (t2g) and two high
energy orbitals (eg)
 We can obtain the information about how a given orbital (p, d, f ….) split in a
Character table for Oh point group
given field directly from character table. linear,
3C2
Oh E 8C3 6C2 6C4
=(C4)2
i 6S4 8S6 3σh 6σd rotatio quadratic
ns
A1g 1 1 1 1 1 1 1 1 1 1 x2+y2+z2
A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 (2z2-x2-y2, x2-y2)
(Rx, Ry,
T1g 3 0 -1 1 -1 3 1 0 -1 -1
Rz)
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
(x, y,
T1u 3 0 -1 1 -1 -3 -1 0 1 1
z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1

CHEM 221/
Phy 335
Molecular
Symmetry
 If we know the shape of orbitals, we can Character table for C2v point group
also determine where these orbitals belong in a linear,
given symmetry (point group). rotations
A1 1 1 1 1 z x2, y2, z2
 If we do not know the shape of orbital but A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
know its magnetic quantum number, we can B2 1 -1 -1 1 y, Rx yz
determine the splitting using Symmetry &
Group theory.
Following formulas will be used for the determination of reducible representation
pertaining to splitting of any set of orbitals (p, d, f, g, h…) in any given field (Oh, Td,
D4h etc).
𝜒 𝐸 = 2𝑙 + 1 𝜒 𝑖 = ±(2𝑙 + 1) 𝜒 𝜎 = ±𝑆𝑖𝑛 𝑙 + 1/2 𝜋
𝑆𝑖𝑛 𝑙 + 1ൗ2 𝜃 𝑆𝑖𝑛 𝑙 + 1ൗ2 𝜃 + 𝜋

𝜒𝐶 𝜃 = 𝜒[𝑆 𝜃 ] = ±
𝑆𝑖𝑛 𝜃ൗ2 𝑆𝑖𝑛
(𝜃 + 𝜋)ൗ
2
θ is rotation angle for C & S Orbital s p d f g h ………….
π = 180 l 0 1 2 3 4 5 ………….
+ for gerade & – for ungerade g u g u g u …………
CHEM 221/
Phy 335
Molecular Splitting of d Orbitals in Tetrahedral Symmetry
Symmetry
Tetrahedral Symmetry
𝜒 𝐸 = 2𝑙 + 1 𝜒 𝑖 = ±(2𝑙 + 1) 𝜒 𝜎 = ±𝑆𝑖𝑛 𝑙 + 1/2 𝜋

𝜒𝐶 𝜃 = 𝜒[𝑆 𝜃 ] = ±
(𝜃 + 𝜋)ൗ
2
For d orbital l = 2
𝜒 𝐸 = 2(2) + 1 = 5 5 –1 +1 –1 +1
𝑆𝑖𝑛 2+1Τ2 120 3 3
𝜒 𝐶3 = = sin 300 ÷ sin 60 = − ÷ = −1 After reduction
𝑆𝑖𝑛 120Τ2 2 2
𝑆𝑖𝑛 2+1Τ2 180 1

it becomes
𝜒 𝐶2 = = sin 450 ÷ sin 90 = 1 = 1 E + T2
𝑆𝑖𝑛 180Τ2
𝑆𝑖𝑛 2+1Τ2 90+180 2 2

𝜒 𝑆4 = + = sin 675 ÷ sin 135 = ÷ = −1
𝑆𝑖𝑛 (90+180)ൗ2 2 2
𝜒 𝜎 = + 𝑆𝑖𝑛 2 + 1/2 180 = sin 450 = +1

CHEM 221/
Phy 335
Molecular Splitting of d Orbitals in Tetrahedral Symmetry
Symmetry
Character table for Td point group

linear,
E 8C3 3C2 6S4 6σd quadratic
rotations
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)
d orbitals split in to E + T2

CHEM 221/
Phy 335
Molecular
Splitting of d Orbitals in a Given Symmetry (Point Group)
Symmetry
How the five d orbitals split

in Trigonalbipyramidal field?
linear,
E 2C3 3C'2 σh 2S3 3σv quadratic
rotations
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
E'' 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)

CHEM 221/
Phy 335
Molecular
Symmetry
How the five d orbitals split in Square planar field?

linears,
2C4 quadrati
E C2 2C'2 2C''2 i 2S4 σh 2σv 2σd rotation
(z) c
s
A1g 1 1 1 1 1 1 1 1 1 1 x2+y2, z2
A2g 1 1 1 -1 -1 1 1 1 -1 -1 Rz
B1g 1 -1 1 1 -1 1 -1 1 1 -1 x2-y2
B2g 1 -1 1 -1 1 1 -1 1 -1 1 xy
Eg 2 0 -2 0 0 2 0 -2 0 0 (Rx, Ry) (xz, yz)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 1 -1 -1 -1 -1 -1 1 1 z
B1u 1 -1 1 1 -1 -1 1 -1 -1 1
B2u 1 -1 1 -1 1 -1 1 -1 1 -1
Eu 2 0 -2 0 0 -2 0 2 0 0 (x, y)
CHEM 221/
Phy 335
Molecular
Symmetry
 Short cut:
For groups with large number of operations, you can do

calculations in a proper sub-group and later add g or u signs
i.e. instead of Oh do calculations in O group

Instead of D6h, do calculations in D6 group
Instead of D4h, do calculations in D4 group
And remember to add g or u symbols in your final result.
This short cut is only for splitting of orbitals/terms

CHEM 221/
Phy 335
Molecular
Symmetry
Octahedral Symmetry
𝜒 𝐸 = 2𝑙 + 1 𝜒 𝑖 = ±(2𝑙 + 1) 𝜒 𝜎 = ±𝑆𝑖𝑛 𝑙 + 1/2 𝜋

𝜒𝐶 𝜃 = 𝜒[𝑆 𝜃 ] = ±
(𝜃 + 𝜋)ൗ
2
For d orbital l = 2
We will work in O instead of Oh
5 –1 +1 –1 +1
𝜒 𝐸 = 2(2) + 1 = 5
𝑆𝑖𝑛 2+1Τ2 120 3 3 After reduction
𝜒 𝐶3 = = sin 300 ÷ sin 60 = − ÷ = −1
𝑆𝑖𝑛 120Τ2 2 2
it becomes
𝑆𝑖𝑛 2+1Τ2 180 1
E + T2
𝜒 𝐶2 = = sin 450 ÷ sin 90 = 1 = 1
𝑆𝑖𝑛 180Τ2
Add g into these
𝑆𝑖𝑛 2+1Τ2 90 2 2
𝜒 𝐶4 = + = sin 225 ÷ sin 45 = − ÷ = −1 Eg + T2g
𝑆𝑖𝑛 (90)ൗ2 2 2

CHEM 221/
Phy 335
Molecular
Symmetry
Character table for Oh point group
linear,
3C2
Oh E 8C3 6C2 6C4
=(C4)2
i 6S4 8S6 3σh 6σd rotatio quadratic
ns
A1g 1 1 1 1 1 1 1 1 1 1 x2+y2+z2
A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 (2z2-x2-y2, x2-y2)
(Rx, Ry,
T1g 3 0 -1 1 -1 3 1 0 -1 -1
Rz)
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1
Exercise: Determine the splitting of following

• f orbitals in octahedral, tetrahedral, and square planar geometry
• g orbitals in trigonal bipyramidal and square prismatic geometry
• h orbitals in trigonal prismatic, cubic, and square antiprismatic geometry
CHEM 221/
Phy 335
Molecular
Splitting of f Orbitals in a Given Symmetry (Point Group)
Symmetry
Octahedral Symmetry
𝜒 𝐸 = 2𝑙 + 1 𝜒 𝑖 = ±(2𝑙 + 1) 𝜒 𝜎 = ±𝑆𝑖𝑛 𝑙 + 1/2 𝜋

𝜒𝐶 𝜃 = 𝜒[𝑆 𝜃 ] = ±
(𝜃 + 𝜋)ൗ
2
For f orbital l = 3
After reduction
7 +1 –1 –1 –1
𝜒 𝐸 = 2(3) + 1 = 7 it becomes
𝑆𝑖𝑛 3+1Τ2 120 3 3 A2 + T1 + T2
𝜒 𝐶3 = = sin 420 ÷ sin 60 = + ÷ = +1
𝑆𝑖𝑛 120Τ2 2 2
𝑆𝑖𝑛 3+1Τ2 180 −1

𝜒 𝐶2 = = sin 630 ÷ sin 90 = =−1
𝑆𝑖𝑛 180Τ2 1
Add u into these
𝑆𝑖𝑛 3+1Τ2 90 2 2 A2u + T1u + T2u
𝜒 𝐶4 = = sin 315 ÷ sin 45 = − ÷ ] = −1
𝑆𝑖𝑛 (90)ൗ2 2 2

CHEM 221/
Phy 335
Molecular
Symmetry
Exercise: Determine the splitting of following

• f orbitals in octahedral, tetrahedral, and square planar geometry
• g orbitals in trigonal bipyramidal and square prismatic geometry
• h orbitals in trigonal prismatic, cubic, and square antiprismatic geometry
CHEM 221/
Phy 335
Molecular
Symmetry
 Any symmetry/geometry (other than radial or spherical) in which all the

five d orbital remain degenerate?.
 Think of any geometry which has more symmetry than Oh but less
symmetry than spherical shape?
 Icoshedron  Buckyball
 Any chemical compound/species having Ih symmetry?
 How the metal d orbital will split if placed inside buckyball?
CHEM 221/
Phy 335
Molecular
Symmetry
 All the five d orbital will remain degenerate if placed inside Bucky ball.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Reducible Representation
How to generate reducible representation?
Choose appropriate basis set, and see how many arrows remain
unchanged on applying the group operations.
Tetrahedral shape (arrangement of bond pairs + lone pairs). Point
Basis Set: Four arrows pointing away central atom. Group: Td
Td E 8C3 3C2 6S4 6σd Character table for Td point group
Reducible 4 1 0 0 2 linear,
quadrati
E 8C3 3C2 6S4 6σd rotation
Rep: s
c
A1 1 1 1 1 1 x2+y2+z2
These numbers actually come A2 1 1 1 -1 -1
(2z2-x2-
from matrices i.e. these are the E 2 -1 2 0 0
y2, x2-y2)
trace of matrix for the particular T1 3 0 -1 1 -1
(Rx, Ry,
R z)
operation of the point group (xy, xz,
T2 3 0 -1 -1 1 (x, y, z)
yz)

CHEM 521 &
CHEM 721
Inorganic Representing Point Group Operations by Numbers
Chemistry
Can we represent a symmetry operation by number?

Let us look at the effect on a px orbital
of a C2 rotation about the z axis:
The sign of the px orbital is changed, so how
Answer = 1
can the operation be represented, by +1 or –1?
px becomes –px or: C2Px = –lPx
What number will represent the operation σ(xz)? +1 i.e. σ(xz) px = lpx
What happens to the py orbital on
application of a clockwise C4 about
the z axis?
What number should we assign to
application of a clockwise C4
rotation about the z axis?
We can use matrices to address such problems?
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrices
Matrices are very helpful for representing symmetry opertaions.
 How to represent symmetry operations in the form of matrices,
and
 How to generate a reducible representation from matrices.
But before that we should know what matrices are and how are
they multiplied.

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrices
A matrix is an ordered
array of numbers, such as
Matrix Multiplication:
 In general, matrix multiplication, unlike arithmetic multiplication,
is not commutative, which means the multiplication of matrix A
and B, given as AB, cannot be equal to BA, i.e., AB ≠ BA.
 Therefore, the order of multiplication for the multiplication of
matrices is important.
 In linear algebra, the multiplication of matrices is possible only
when the matrices are compatible.
To multiply matrices, the number of
vertical columns of the first matrix
must be equal to the number of
horizontal rows of the second matrix.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Matrix Multiplication
To find the product, add, term by term, the products of each row of
the first matrix by each column of the second (each term in a row
must be multiplied by its corresponding term in the appropriate
column of the second matrix). Place the resulting sum in the product
matrix with the row determined by the row of the first matrix and the
column determined by the column of the second matrix:.
Here,

CHEM 521 &
CHEM 721
Inorganic
Chemistry
To multiply matrices, the number of
vertical columns of the first matrix
must be equal to the number of
horizontal rows of the second
matrix.
Here,
This example has two rows and two columns in each initial matrix, so
it has two rows and two columns in the product matrix.
CHEM 521 &
CHEM 721
Inorganic
Chemistry
[(1)(1) + (2)(0) + (3)(0) (1)(0) + (2)(-1) + (3)(0) (1)(0) + (2)(0) + (3)(1)]i = [1 -2 3]i
Here, i = 1, j = 3, and k = 3, so the product matrix has one row (i) and
three columns (j).
Here i = 3, j = 1, and k = 3, so the product matrix has three rows ( i )

and one column (j).
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Exercise. Do the following multiplications:

CHEM 521 &
CHEM 721
Chemistry

Each symmetry operation can be expressed as a transformation

matrix as follows:

CHEM 521 &
CHEM 721
Chemistry

Each symmetry operation can be expressed as a
transformation matrix as follows:
As examples, consider how transformation matrices can be used to
represent the symmetry operations of the C2v point group:
C2: Rotate a point having coordinates (x, y, z) about the C2(z) axis.
The new coordinates are given by.
New X = 1xX + 0xY + 0xZ
Transforma
tion matrix New Y = 0xX + 1xY + 0xZ
for C2.
New Z = 0xX + 0xY + 1xZ

CHEM 521 &
CHEM 721
Chemistry

C2: Rotate a point having coordinates (x, y, z) about
the C2(z) axis. The new coordinates are given by.
In matrix notation,

CHEM 521 &
CHEM 721
Chemistry
σxz: Reflect a point with coordinates (x, y, z)

through the xz plane.
Transformation matrix for σxz.
In matrix notation,

CHEM 521 &
CHEM 721
Chemistry

operations of the group are
We call this a matrix representation of the C2v point group.

These matrices combine in the same way as the operations themselves.

CHEM 521 &
CHEM 721
Chemistry

operations of the C2v group are
The character, defined only for a square matrix, is the trace of the
matrix, or the sum of the numbers on the diagonal from upper left to
lower right.
For the C2v point group, the following characters are obtained from
the preceding matrices:

CHEM 521 &
CHEM 721
Chemistry
Consider the C3 rotation shown in Figure

Counterclockwise rotation of 120° results
in a new x’ and y’ as shown, which can be
described in terms of the vector sums of x
and y by using trigonometric functions:
The transformation matrices for the C3 symmetry operations is:

CHEM 521 &
CHEM 721
Chemistry
General case: x’ = x cos θ – y sin θ

y’ = x sin θ + y cos θ
For C3: θ = 2π/3 = 120°

General Transformation Matrix for proper
rotation (anti clockwise) by θ° about z axis:
Cn = Where θ = 2π/n
General Transformation Matrix

for improper rotation (anti Sn =
clockwise) by θ° about z axis:
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Vector Basis for Td
 All operations of Td simply interchange vectors,
so we may follow the effects of each operation by
noting the transformations of the vector tips, A, B,
C, and D.
 The character generated by any operation of a
class is the same as all other members of the class.
 We do not need to subject the set to all h = 24 operations of the
group Td , just one operation from each of the five classes of
operations: E, 8C3 , 3C2 , 6S4 , σd.
 We can describe the effect of each representative operation by a
4x4 transformation matrix that shows how A, B, C, and D are
interchanged.
 The traces of the matrices will give us the characters of reducible
representation.
CHEM 521 &
CHEM 721
Inorganic
Chemistry

CHEM 521 &
CHEM 721
Inorganic
Chemistry
Gathering all reducible characters from the trace of each matrix

we find the following:

&
Fall 2021

LUMS
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Recap
Splitting of Orbitals/Term Symbols in a Given Symmetry (Point Group)
Following formulas will be used for the determination of reducible representation pertaining
to splitting of any set of orbitals (p, d, f, g ..) in any given field (Oh, Td, D4h etc).
𝜒 𝐸 = 2𝑙 + 1 𝜒 𝑖 = ±(2𝑙 + 1) 𝜒 𝜎 = ±𝑆𝑖𝑛 𝑙 + 1/2 𝜋

𝜒𝐶 𝜃 = 𝜒[𝑆 𝜃 ] = ±
(𝜃 + 𝜋)ൗ
2
θ is rotation angle for C & S Orbital s p d f g h ………….
π = 180 l 0 1 2 3 4 5 ………….
+ for gerade & – for ungerade g u g u g u …………
 Matrix Multiplication
 Symmetry Operations: Matrix Representations

CHEM 521 &
CHEM 721
Inorganic Recap: Generation of Reducible Representation
Chemistry
Hybridization Determination of orbitals suitable for hybridization

for a given geometry Basis set
Td E 8C3 3C2 6S4 6σd
Reduced to: A1+T2
A1 = s and T2 = (px, py, pz) or (dxy,dyz, dzx) Two Possible combinations
s, px, py, pz i.e. sp3 as in CH4, and s, dxy, dyz, dzx i.e. sd3 as in CrO42+ ion
Splitting of Orbitals/Term Symbols in a Given Symmetry (Point Group)
Tetrahedral Symmetry
𝜒 𝐸 = 2𝑙 + 1 𝜒 𝑖 = ±(2𝑙 + 1) 𝜒 𝜎 = ±𝑆𝑖𝑛 𝑙 + 1/2 𝜋

𝜒𝐶 𝜃 = 𝜒[𝑆 𝜃 ] = ±
(𝜃 + 𝜋)ൗ
2
After reduction it becomes

5 –1 +1 –1 +1 E + T2
CHEM 521 &
CHEM 721
Inorganic
Chemistry
Learning Outcome
Molecular Symmetry
 Predicting the number of IR and Raman active vibrations.
 Which of these gases has greater Global Warming Potential?

a. CO2
b. CH4
 What if we can convert CO2 to CH4 using electricity?

CHEM 221/
Phy 335
Molecular
Symmetry
Vibrational Spectroscopy
Infrared (IR) and Raman spectroscopies are branches of vibrational
spectroscopy.
Infrared spectroscopy (IR spectroscopy) involves the interaction of infrared
radiation with matter.
https://en.wikipedia.org/wiki/Infrared_spectroscopy
IR spectroscopy is often used to identify structures because functional

groups give rise to characteristic bands both in terms of intensity and
position (frequency).

CHEM 221/
Phy 335
Molecular
Symmetry
Infrared (IR) and Raman spectroscopies are branches of vibrational
spectroscopy.
https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemistry_Textboo
k_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Spectroscopy/Vi
brational_Spectroscopy/Vibrational_Modes/Introduction_to_Vibrations
Knowledge of symmetry is very helpful for studying vibrational

spectroscopy.
 We will derive the number of vibrational modes for some simple
molecules
 We will also determine whether these modes are infrared (IR) and/or
Raman active (i.e. whether absorptions corresponding to the vibrational
modes are observed in the IR and/or Raman spectra).
CHEM 221/
Phy 335
Molecular
Symmetry
How many vibrational modes are there for a given molecular species?
Vibrational spectroscopy is concerned with the observation of the degrees of
vibrational freedom, the number of which can be determined as follows.
The motion of a molecule containing N atoms can conveniently be described
in terms of the three Cartesian axes. The molecule (having N atoms) has 3N
degrees of freedom which together describe the translational, vibrational
and rotational motions of the molecule.
 Total degrees of freedom = 3N
 Translational degrees of freedom = 3
 Remaining (vibrational & rotational) degrees of freedom = 3N – 3
For a non-linear molecule there are three degrees of rotational freedom, but
for a linear molecule, there are only two degrees of rotational freedom.
 Vibrational degrees of freedom (non-linear molecule) = 3N – 6
 Vibrational degrees of freedom (linear molecule) = 3N – 5
CHEM 221/
Phy 335
Molecular
Symmetry
 Vibrational degrees of freedom (non-linear molecule) = 3N –6
 Vibrational degrees of freedom (linear molecule) = 3N –5
How many vibrational modes are there for CO2?
The linear CO2 molecule has four normal modes of vibration.
Two of the modes are degenerate; i.e. they possess the same energy and
could be represented in a single diagram with the understanding that one
vibration occurs in the plane of the paper and another, identical in energy,
takes place in a plane perpendicular to the first.
Triatomic nonlinear
molecule such as SO2 has
three vibrational degrees of
freedom.
CHEM 221/
Phy 335
Molecular
Symmetry
Exercise
• How many degrees of vibrational freedom do each of the following

possess: SiCl4, BrF3, POCl3?
• Using the VSEPR model to help you, draw the structures of CF4,
XeF4 and SF4. Assign a point group to each molecule. Show that the
number of degrees of vibrational freedom is independent of the
molecular symmetry.

CHEM 221/
Phy 335
Molecular Selection Rules for an IR Active Mode of Vibration
Symmetry
An IR spectrum records the frequency of a molecular vibration, i.e. bond

stretching and molecular deformation (e.g. bending) modes. However, not all
modes of vibration of a particular molecule give rise to observable
absorption bands in the IR spectrum. This is because the following selection
rule must be obeyed:
For a mode of vibration to be infrared (IR) active, it must give rise to a
change in the molecular electric dipole moment.
Number of degrees of vibrational freedom for CO2 = 3N – 5 = 9 – 5 = 4

The four fundamental modes of vibration are shown in Figure. Although
both the asymmetric stretch and the bend give rise to a change in dipole
moment (generated transiently as the vibration occurs), the symmetric stretch
does not. Thus, only two fundamental absorptions are observed in the IR
spectrum of CO2.
CHEM 221/
Phy 335
Symmetry
For a mode of vibration to be infrared (IR) active, it must give rise to a

change in the molecular electric dipole moment.
Number of degrees of vibrational freedom for SO2 = 3N – 6 = 9 – 6 = 3
All three normal modes of vibration of SO2 all give rise to a change in
molecular dipole moment and are therefore IR active.
 A comparison of these results for CO2 and SO2 illustrates that vibrational
spectroscopy can be used to determine whether an X3 or XY2 species is
linear or bent.
 Linear molecules of the general type XYZ (e.g. OCS or HCN) possess
C∞v symmetry and their IR spectra are expected to show two
absorptions: asymmetric stretching and bending modes are IR active.

CHEM 221/
Phy 335
Symmetry
Exercise
• The IR spectrum of SnCl2 exhibits absorptions at 352, 334 and 120 cm–1.
What shape do these data suggest for the molecule, and is this result
consistent with the VSEPR model?
• The vibrational modes of XeF2 are at 555, 515 and 213 cm–1 but only two
are IR active. Explain why this is consistent with XeF2 having a linear
structure.
• How many IR active vibrational modes does CS2 possess, and why?
• The IR spectrum of SF2 has absorptions at 838, 813 and 357 cm–1.
Explain why these data are consistent with SF2 belonging to the C2v rather
than D∞h point group.
• To what point group does F2O belong? Explain why the vibrational modes
at 928, 831 and 461 cm–1 are all IR active.
CHEM 221/
Phy 335
Molecular
Symmetry
Selection Rule for Raman Spectroscopy
A different selection rule applies to Raman spectroscopy:
For a mode of vibration to be Raman active, it must give rise to a change in
the polarizability of the molecule.
Polarizability is the ease with which the electron cloud associated with the
molecule is distorted.
In addition to these two selection rules, molecules with a center of symmetry
(e.g. linear N2, CO2, and octahedral SF6) are subject to the rule of mutual
exclusion:
For centrosymmetric molecules, the rule of mutual exclusion states that
vibrations that are IR active are Raman inactive, and vice versa.
In the case of a triatomic molecule (bent and asymmetric linear), it is simple
to deduce that the three modes of vibration are composed of two stretching
modes (symmetric and asymmetric) and a bending mode. However, for
larger molecules it is not so easy to visualize the modes of vibration.
CHEM 221/
Phy 335
Molecular
Symmetry
Water (C2v Symmetry)
Because the study of vibrations is the study of
motion of the atoms in a molecule, we must first
attach a set of x , y , and z coordinates to each atom.
For convenience, we assign the z axes parallel to the C2 axis of the molecule,
the x axes in the plane of the molecule, and the y axes perpendicular to the
plane.
Each atom can move in all three directions, so a total of nine transformations
(motion of each atom in the x , y , and z directions) must be considered.
We will use transformation matrices to determine the symmetry of all nine

motions within the C2v point group and then assign them to translation,
rotation, and vibration. Fortunately, it is only necessary to determine the
characters of the transformation matrices (and only one matrix for a
symmetry operation of a unique class), not the individual matrix elements.
CHEM 221/
Phy 335
Molecular
Symmetry
The full 9 * 9
matrix for C2 is
shown as an
example.
Similarly the effect of identity operation E, and two sigma planes can be
shown by 9 * 9 matrices.
What about pyridine with 11 atoms, we would need 33*33 matrices for
each of the four C2v group operations. What about Cr(CO)6?
Fortunately, it is only necessary to determine the characters of the
transformation matrices (and only one matrix for a symmetry operation of a
unique class), not the individual matrix elements.
CHEM 221/
Phy 335
Molecular
Symmetry
For reducible representation for all the molecular
motions, determine how many arrows remain
unchanged.
The reducible
representation for
all motions of the
water molecule is
therefore reduced to
3A1 + A2 + 3B1 +
2B2.

CHEM 221/
Phy 335
Molecular
Symmetry
The reducible
representation for all
motions of the water
molecule is therefore
reduced to
3A1 + A2 + 3B1 +
2B2

CHEM 221/
Phy 335
Molecular
Symmetry
For a mode of
vibration to be
infrared (IR) active,
All motions = 3A1 + A2 + 3B1 + 2B2 it must give rise to a
change in the
Translational = A1 + B1 + B2
molecular electric
Rotational = A2 + B1 + B2 dipole moment.
Vibrational = 2 A1 + B1
In group theory terms, a vibrational mode is active in the infrared if it corresponds to
an irreducible representation that has the same symmetry (or transforms) as the
Cartesian coordinates x , y , or z , because a vibrational motion that shifts the center
of charge of the molecule in any of the x , y , or z directions results in a change in
dipole moment. Otherwise, the
vibrational mode is not infrared active.
2 A1 Both are IR active
B1 IR active
Hence total three peaks in IR spectrum.
All three vibrations are also Raman
active i.e. three peaks in Raman
CHEM 221/
Phy 335
Molecular
Symmetry
IR Spectrum of Water (C2v Symmetry)
(a) Calculated IR
spectrum of
gaseous H2O
showing the three
fundamental
absorptions.
Experimental values
are 3756, 3657 and
1595 cm–1.
(b) IR spectrum of
liquid H2O.

CHEM 221/
Phy 335
Molecular
Symmetry
Vibrations in XeF4 (D4h Symmetry)
Using the x , y , and z coordinates for each atom in XeF4, determine the
reducible representation for all molecular motions; reduce this
representation to its irreducible components; and classify these
representations into translational, rotational, and vibrational modes.
First, it is useful to assign x , y , and z coordinate axes to each atom.
It is essential to recognize that only the coordinates on atoms that do

not move when symmetry operations are applied can give rise to
nonzero elements along the diagonals of transformation matrices.
CHEM 221/
Phy 335
Molecular
Symmetry
It is essential to recognize that only the coordinates on atoms that do

not move when symmetry operations are applied can give rise to
nonzero elements along the diagonals of transformation matrices.
For example, if a symmetry operation applied
to XeF4 causes all F atoms to change position,
these atoms cannot give rise to elements along
the diagonal, so they can be ignored; only
coordinates of Xe would need to be considered.
In addition: If a symmetry operation leaves the direction of a coordinate
unchanged, it gives a character of 1 along the diagonal.
For example, the identity operation on XeF4 leaves the coordinates x , y ,
and z unchanged; each of these has a diagonal element of 1 for each atom.

CHEM 221/
Phy 335
Molecular
Symmetry
It is essential to recognize that only the coordinates on atoms that do not move
when symmetry operations are applied can give rise to nonzero elements along
the diagonals of transformation matrices.
If a symmetry operation reverses the
direction of a coordinate, this corresponds
to a diagonal element of -1.
The σh operation on XeF4 reverses the
direction of the z axis for each atom.
If a symmetry operation transforms a coordinate into another

coordinate, this gives a diagonal element of zero.
If XeF4 is rotated about its C4 axis, the x and y coordinates of Xe are
interchanged; they contribute zero to the character.
CHEM 221/
Phy 335
Molecular
Symmetry
Using the x , y , and z coordinates for each atom in XeF4, determine
the reducible representation for all molecular motions; reduce this
representation to its irreducible components; and classify these
representations into translational, rotational, and vibrational modes.
15 1 –1 –3 –1 –3 –1 5 3 1
The character under E indicates that there are 15 possible motions to be considered.
This representation reduces to

CHEM 221/
Phy 335
Molecular Translational Motion in XeF4 (D4h Symmetry)
Symmetry
This is motion through space with x , y , and z components. The irreducible

representations matching these components have the labels x , y , and z on
the right side of the D4h character table: A2u (matching z ) and Eu (doubly
degenerate, matching x and y together). These three motions can be
represented as shown in

CHEM 221/
Phy 335
Molecular
Symmetry
Rotational Motion in XeF4 (D4h Symmetry)
This type of motion can be factored into rotation about the mutually
orthogonal x, y, and z axes. The matching expressions in the character table
are Rx, Ry, and Rz, representing rotation about these three axes, respectively.
The irreducible representations are A2g (Rz, rotation about the z axis), and
Eg (Rx, Ry), doubly degenerate rotations about the x and y axes) as shown in
figure.

CHEM 221/
Phy 335
Molecular
Symmetry
15 1 –1 –3 –1 –3 –1 5 3 1
The character under E indicates that there are 15 possible motions to be considered.
This representation reduces to
Trans = –A2u –Eu

Rot = –A2g –Eg
Vib = A1g B1g B2g A2u B2u 2Eu
The remaining nine motions (15 total – 3

translations – 3 rotations) are vibrational.
They involve changes in bond lengths
and angles and motions both within and
out of the molecular plane.

CHEM 221/
Phy 335
Molecular
Symmetry
IR = No No No Yes No Yes 3 Peaks
Raman = Yes Yes Yes No No No 3 Peaks

For centrosymmetric molecules, the rule of mutual exclusion states that
vibrations that are IR active are Raman inactive, and vice versa.

CHEM 221/
Phy 335
Molecular
Symmetry
IR = No No No Yes No Yes 3 Peaks
Raman = Yes Yes Yes No No No 3 Peaks
For centrosymmetric molecules, the rule of mutual exclusion states that vibrations
that are IR active are Raman inactive, and vice versa.

CHEM 221/
Phy 335
Molecular
Symmetry
Vibrations in NH3 (C3v Symmetry)
Determine the number of peaks, their symmetries, and the infrared
and Raman activities of the vibration modes of ammonia molecule.
Point Group: C3v
Basis Set: X, Y, Z coordinates on each atom.
Note: We do not need to make 12 x 12 matrices,
but We need to remember the contribution of
diagonal elements for C3 operations in this case.
Reducible Representation.
12 0 2
Reduced to 3A1 + A2 + 4E (3+1+4x2 = 12 Total degrees of motion i.e. 3N)

CHEM 221/
Phy 335
Molecular
Symmetry
Vibrations in NH3 (C3v Symmetry)
Reducible Representation.
12 0 2
Reduced to 3A1 + A2 + 4E (12 Total degrees of freedom)
Total Motions = 3A1 + A2 + 4E
Trans = –A1 –E based on the x , y , & z entries in the table
Rot = –A2–E based on the Rx , Ry , and Rz entries

in the table
Vib = 2A1 2E remaining from the total;
Vib = A1 + A1 + E + E 1+1+2+2 = 6 i.e. 3N-6 = 6
Remember E is doubly degenerate
IR Active = Yes + Yes + Yes + Yes hence 4 peaks in IR
Raman Active = Yes + Yes + Yes + Yes all 4 should be Raman active
Result: 4 peaks in IR

CHEM 221/
Phy 335
Molecular
Symmetry
Both have the same trace and hence grouped together in C3v.

CHEM 221/
Phy 335
Molecular
Symmetry
Reducible Representation without Matrices
It is rather troublesome to work out the sines and cosines for each individual
case.
It is easier to consider the atoms in two sets for each symmetry operation:
Set # i. Atoms which are shifted by the operation contribute nothing to the
character of the Cartesian representation.
Set # ii . Each atom shifted by the operation contributes an amount f(R) to
the character of the Cartesian representation where f(R) depends on the
operation as follows:
Operation: E σ i C2 C3 C4 C5 C6 S3 S4 S5 S6 S8
f(R): 3 1 –3 –1 0 1 1.618 2 –2 –1 0.382 0 0.414
Q. Use the above table to set up the characters of the Cartesian representation
of CH4: Td: E 8C3 3C2 6S4 6σd Reduced to: A1+E+T1+3T2
15 0 –1 –1 3 Trans = T2 Rot = T1
Nine vibrations (3N-6 = 9 for CH4) with symmetries A1 + E + 2T2.
Only two T2 are IR active i.e. two peaks in IR (each is triply degenerate)
CHEM 221/
Phy 335
Molecular
Symmetry
Vibrational Spectroscopy: Exercise
Q. The IR spectrum of BF3 shows absorptions at 480, 691 and 1449 cm–1.
Use these data to decide whether BF3 has C3v or D3h symmetry.
Q. In the IR spectrum of NF3, there are four absorptions. Why is this
consistent with NF3 belonging to the C3v rather than D3h point group?
Q. The IR spectrum of BrF3 in an argon matrix shows six absorptions.
Explain why this observation confirms that BrF3 cannot have C3v symmetry.
Q. The IR spectrum of gaseous ZrI4 shows absorptions at 55 and 254 cm–1.
Explain why this observation is consistent with molecules of ZrI4 having Td
symmetry.
Q. The [PdCl4]2 ion gives rise to three absorptions in its IR spectrum (150,
321 and 161 cm–1). Rationalize why this provides evidence for a D4h rather
than Td structure.
Q. SiH2Cl2 is described as having a tetrahedral structure; SiH2Cl2 has eight
IR active vibrations. Comment on these statements.

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Advance Inorganic

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CHEM 521 - Advanced Inorganic Chemistry I

Lecture 05, Tuesday, Sept 21, 2021

Dr. Ghayoor Abbas Chotana

Department of Chemistry and Chemical Engineering

Additional Notes Dr. Ghayoor Abbas

 Improper Rotation (Examples, Number of unique operations)

 Application of symmetry in predicting optical activity.

Additional Notes Dr. Ghayoor Abbas

, e.g. ethane in the staggered conformation has an S6 axis because it

N.B. Neither C6 nor σh are present on their own in Ethane Staggered.

 S61  S62  S63

 S61 = Unique  S62 = C31  S63 = i

 Which of these operations are unique?

List all the (Unique) symmetry operations in Ammonia?

Half i.e. 3 proper rotations (C31 and C32 + E=C33).

List all the (Unique) symmetry operations in [PtCl4]2?

Improper rotations: i, 2S4 (S41 and S43), σh, 2σv, 2σd

Total sixteen operations.

Half i.e. 8 proper rotations. And half i.e. 8 improper rotations

 Any molecule will generally have EVEN number of total

List all the (Unique) symmetry operations in Benzene?

Chapter 1: Alan Vincent Dr. Ghayoor Abbas

3 C2 (This C2 is co-linear with C4 principal axis)

8 C3 (This C3 passes through the middle of two C2

opposite faces. Since there are 8 faces in

Lecture 06, Thursday, Sept 23, 2021

Dr. Ghayoor Abbas Chotana

Department of Chemistry and Chemical Engineering

 Improper Rotation (Examples, Number of unique operations in

Additional Notes Dr. Ghayoor Abbas

 Group together molecules of same symmetry in Point Groups

Additional Notes Dr. Ghayoor Abbas

List all the (Unique) symmetry operations in Benzene?

Chapter 1: Alan Vincent Dr. Ghayoor Abbas

Chapter 1: Alan Vincent Dr. Ghayoor Abbas

3 C2 (This C2 is co-linear with C4 principal axis)

8 C3 (This C3 passes through the middle of two C2

opposite faces. Since there are 8 faces in

 Maleic acid or Phthalic acid

Point Group = C2v

E, C2, σ, σ' Point Group = C2v

For example Trans Ethene C2 + σh = C2h

For example water C2 + σv = C2v

For example hydrogen peroxide (H2O2), C2 + No σ = C2

Chapter 2: Alan Vincent Dr. Ghayoor Abbas

Chapter 2: Alan Vincent Dr. Ghayoor Abbas

Chapter 2: Alan Vincent Dr. Ghayoor Abbas

i.e. Linear molecule + inversion center present = D∞h

For example H2, N2 etc.

i.e. Linear molecule + inversion center absent = C∞v

For example HCl, HCN etc.

Systematic Classification of Molecules

Chapter 2: Alan Vincent Dr. Ghayoor Abbas

Chapter 2: Alan Vincent Dr. Ghayoor Abbas

Chapter 2: Alan Vincent Dr. Ghayoor Abbas

Lecture 07, Tuesday, Sept 28, 2021

Dr. Ghayoor Abbas Chotana

Department of Chemistry and Chemical Engineering

Additional Notes Dr. Ghayoor Abbas

Additional Notes Dr. Ghayoor Abbas

For example Trans Ethene C2 + σh = C2h

For example water C2 + σv = C2v

For example hydrogen peroxide (H2O2), C2 + No σ = C2

Chapter 2: Alan Vincent Dr. Ghayoor Abbas