Class 02 Advanced Inorganic Chemistry

Inorganic Chemistry

Symmetry & Group Theory

Chemical Applications of Group Theory, 3rd ed. F. Albert Cotton, 1990

Yunho Lee, Ph.D. 02/14/2012

Department of Chemistry Korea Advanced Institute of Science and Technology

A mathematical Group is a collection of elements that are interrelated according to certain rules. Identity
1. Identity element (E): one element in the group must commute with all elements and leave them unchanged. EX = XE = X 2. Every element must have a reciprocal. AA-1 = A-1A = E (ABC..XY)-1 = X-1Y-1..C-1B-1A-1

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Inverse

Closure

3. The product (combination) of any two elements and the square of each element must be an element in the group. AB or BA are they the same? Multiplication is commutative. xy = yx and 3 x 6 = 6 x 3 However, in the group theory, the commutative law does not in general hold. AB = C while BA = D, where C and D are two more elements in the group. 4. The associative law of multiplication must hold.

Associativity

A(BC) = (AB)C

Point Groups

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A The set of symmetry operations describing the molecules overall symmetry is called the point group of the molecule.
Group with low order symmetry: C1, Cs, Ci Group with high order symmetry: Cv, Dh, Td, Oh, Ih D group: Dnh, Dnd, Dn C or S2n group: Cnh, Cnv, S2n, Cn 1. E,
Oh

48 operations

2. 4C3, 4C32, 3. 6C2, 4. 3C4, 3C43, 5. 3C42, 6. i, 7. 3S4, 3S43, 8. 4S6, 4S65, 9. 3h, 10. 6d

Point Groups
1. E
F1 F6 F4 F2 S F3 F5

Oh
F1

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F6 F4

S F2

F3 F5

2. 4C3, 4C32
F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 S F3 F5 S F3 F5 S F3 F5 S F3 F5 F3

C3

F2 F6

S F4 F3

F5 F1

C32

F5 F4 F2 F6 F6 F3 F2 F5 F6 F4 F1 F5 F4 F2 F5 F3 S F6 F1 S F2 F3 S F1 F4 S F1 F3

C3

F1 F5

S F4 F4

F6 F2

C32

C3

F1 F6

S F3 F5

F5 F2

C32

C3

F3 F1

S F6

F2 F4

C32

F6 F4

Point Groups
F5 F2

F3

C3

F3 F1

S F6

F2 F4

C3

F2 F5

S F3

F6 F1
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Oh
C2

3. 6C2
F6 F4

F1 S F2 F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 S F3 F5 S F3 F5 S F3 F5 S F3 F5 S F3 F5 F3 F5 F4 F6

F2 S F1 F2 F5 F3

Additional three C2 will be counted as C42

F6 F4

C2

F3 F5

S F1 F3

C2

F5 F2

S F4 F4

F1 F6

C2

F5 F1

S F3 F6

F2 F6

C2

F1 F3

S F5 F5

F4 F2

C2

F2 F3

S F6

F4 F1

Point Groups
4. 3C4, 3C42, 3C43
F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 S F3 F5 S F3 F5 S F3 F5

Oh

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F1

C4

F3 F6

S F2 F6

F5 F4

C42

F1 F5 F3 F2 F2 F5 F4 F1 F2 F6 F3 F1 S F4 F5 S F3 F6 S F4 F6

C43

F1 F4 F5 F2 F5 F1 F4 F6 F4 F6 F2 F3 S F1 F5 S F3 F2 S F6 F3

C4

F2 F4

S F5 F3

F3 F1

C4

C4

C4

F6 F1

S F4

F2 F5

C4

C4

5. i
F1 F6 F4 F2 S F3 F5 F2

F5 F3

S F1

F4 F6

Point Groups
6. 3S4, 3S43
F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 S F3 F5 S F3 F5 S F3 F5

Oh
The same as C42
F2 F5 F4 F1 F6

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S4

F3 F6

S42

F1 F5 F3 F2 F2 F5 F4 F1 F2 F6 F3 F1 S F4 F5 S F3 F6 S F4 F6

S43

F2 F4 F5 F1 F5 F1 F3 F6 F4 F5 F2 F3 S F1 F6 S F4 F2 S F6 F3

S4

F2 F3

S F5 F3

F4 F1

S42

S43

S4

F5 F1

S F4

F2 F6

S42

S43

7. 4S6, 4S65
F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 F1 F6 F4 F2 S F3 F5 F6 F4 F2 S F3 F5 F3 F6 F2 F1 F3 F5 S F3 F5 F1 F4 F6 F1 F5 F4 S F3 F5 F6 F1 F4 F5 F3 F2 F3 F2 F5 F2

The same as C31 S6

F3 F6 F1 F3 F5 F4

The same as i S63

F4 F5 F2 F3 F6 F2 F3 F5 F2 F4 F5 F1 F2 F5 F3 F1 F4 F6 F6 F3 F4 F1 F1 F6

The same as C32 S6 4

F1 F4 F5 F2 F4 F6 F2 F3 F6 F2 F4 F5 F4 F2 F5 F3 F6 F1 F3 F1 F1 F5 F6 F3

S62

F5 F2 F3 F6 F2 F3 F5 F1 F4 F5 F1 F3 F5 F3 F1 F6 F2 F4 F2 F6 F6 F4 F4 F1

S65

F6 F1 F4 F5 F1 F4 F6 F2 F3 F6 F2 F4 F6 F4 F2 F5 F1 F3 F1 F5 F5 F3 F3 F2

S6

F5 F1 F4 F5

F2 F6

S62

S63

S6 4

S65

S6

F1 F3 F6 F3

F4 F2

S6 2

S6 3

S64

S65

S6

F1 F6 F4

F5 F2

S6 2

S6 3

S64

S65

8. 3!h

Point Groups
F1 S F2 F1 F6 F4 F3 F5 F6 F4 F2 F3 F5

F2

F2

F6

F3 F5 F2 F1 F4
S F2

F1 F2 F5 F! 3 F4

F5 F4 F2
F1
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S6

Oh

F3 F1 F6 F4 F5 F2

S62 6!dF3 9.
F1

S6 3
F3 F5

S64
F4 F6 F2 F1 S

F6
F5 F3 F3

S65

F4 F2

F6 F6

F6 F1

F5

F1

F4 F1

8. 3!h
F6 F4

F1 S F2 F1 F6 F4 F2 F1 F6 F4 F2 S F3 F5 S F3 F5 F3 F5

!h

F2 F6 F4 F1 F1 F5 F4 F2 S F3 F6 S F3 F5

F6 F4

S F2 F1

F3 F5

!d

F3 F5

S F2 F3

F6 F4

!h

F6 F4

S F2 F1

F3 F5

!d

F6 F2

S F4 F4

F1 F5

!h

F1 F6 F3 F2 S F4 F5

F6 F4

S F2 F1

F3 F5

!d

F6 F1

S F3 F6

F2 F5

F6 F4

S F2 F1

F3 F5

!d

F1 F4

S F5 F5

F3 F2

F6 F4

S F2

F3 F5

!d

F2 F4

S F6

F3 F1

Point Groups
Oh

48 operations

1. E 2. 4C3, 4C32 3. 6C2 4. 3C4, 3C43 5. 3C42 (=3C2) 6. i 7. 3S4, 3S43 8. 4S6, 4S65 9. 3h 10. 6d

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A group may be separated into smaller sets called classes. To arrange the operations of a symmetry group into sets of equivalent operations. Theses sets will be the classes.
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Classes
A group may be separated into smaller sets called classes.

Inorganic Chemistry

To arrange the operations of a symmetry group into sets of equivalent operations. Theses sets will be the classes. A complete set of elements that are conjugate to one another is called a class of the group.
If A and X are in a group, B = X-1 A X A and B are conjugate.

- Similarity transformations refer to a matrix transformation that results in a similarity. (i) Every element is conjugate with itself. (ii) If A is conjugate with B, then B is conjugate with A. (iii) If A is conjugate with B and C, then B and C are conjugate with each other.

 Representations of C2v Point Groups

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C2

v(xz)

v(yz)

1 0 0

0 1 0

0 0 1

-1 0 0

0 -1 0

0 0 1

1 0 0

0 -1 0

0 0 1

-1 0 0

0 1 0

0 0 1

Character table for C2v

C2v B1 B2 A1 A2

C2

v(xz)

v(yz)

1 1 1 1

-1 -1 1 1

1 -1 1 -1

-1 1 1 -1

x, Ry y, Rx z Rz

xz yx x2, y2, z2 xy
11

 Character Table of Groups

Schoenflies symbol for the group Classes Character table for C2v

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C2v B1 B2 A1 A2

C2

v(xz)

v(yz)

1 1 1 1

-1 -1 1 1

1 -1 1 -1

-1 1 1 -1

x, Ry y, Rx z Rz

xz yx x2, y2, z2 xy

Area II

Area I

Area III

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Area I

Character Table of Groups

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Properties of Characters of Irreducible Rep. in the Point Group

1. Order (h) 2. Classes 3. # of irreducible representations = # of classes 4. Dimension: The sum of (Dimension)2 = h 5. The sum of (Character)2 # of operations in the class = h 6. Irreducible representations are orthogonal each other! The sum of the products of any two representations multiplied by the number of operations in each class equals zero. 7. A totally symmetric representation is included in all groups.

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Area I

Character Table of Groups

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1. Order (h): The total # of symmetry operations in the group E, C2, v(xz), v(yz) h = 4 2. Classes: symmetry operations arranged by class 3. # of irreducible representations = # of classes
Character table for C2v E C2 v(xz) v(yz)

B1 B2 A1 A2

1 1 1 1

-1 -1 1 1

1 -1 1 -1

-1 1 1 -1

x, Ry y, Rx z Rz

xz yx x2, y2, z2 xy

Dimension for each irreducible representation

For each irreducible rep,

4. The sum of (Dimension)2 = h

5. The sum of (Character)2 # of operations in the class = h 14

Area I

Character Table of Groups

1.Order, h = 1 + 2 + 3 + 1 + 2 + 3 = 12 2. 6 Classes 3. 6 Classes = 6 irreducible representations

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4. The sum of (Dimension)2 = 1 + 1 + 4 + 1 + 1 + 4 = 12

D3h group

5. The sum of (Character)2 # of operations in the class = 1 (1)2 + 2 (1)2 + 3 (-1)2 + 1 (1)2 + 2 (1)2 + 3 (-1)2 = 12 Character table for D3h
D3h A1 A2 E A1 A2 E E 1 1 2 1 1 2 2C3 1 1 -1 1 1 -1 3C2 1 -1 0 1 -1 0 h 1 1 2 -1 -1 -2 2S3 1 1 -1 -1 -1 1 3v 1 -1 0 -1 1 0 15

 Molecular Vibrations of Water

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- Modes of vibration of molecules can be determined by symmetry! - Water has C2v symmetry - C2 axis is parallel to z axis.
x

y E C2 v(xz) v(yz)

1 0 0

0 1 0

0 0 1

-1 0 0

0 -1 0

0 0 1

1 0 0

0 -1 0

0 0 1

-1 0 0

0 1 0

0 0
16

 Molecular Vibrations of Water

E operation x 1 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 x y z x y z x y z

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y z x

0 0 0

Ha Hb

y z x y z

0 0 0

Ha Hb
17

0 0

Character () = 9

 Molecular Vibrations of Water

C2 operation x -1 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 -1 0 0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 x y z x y z x y z

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y z x

0 0 0

Ha Hb

y z x y z

0 0 0

Ha Hb
18

0 0

Character () = -1

 Molecular Vibrations of Water

v(xz) operation x 1 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 0 1 x y z x y z x y z

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y z x

0 0 0

Ha Hb

y z x y z

0 0 0

Ha Hb
19

0 0

Character () = 3

 Molecular Vibrations of Water

v(yz) operation x -1 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 -1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 x y z x y z x y z

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y z x

0 0 0

Ha Hb

y z x y z

0 0 0

Ha Hb
20

0 0

Character () = 1

 Molecular Vibrations of Water

Inorganic Chemistry

- Irreducible rep. represents all molecular motions; 3 translations, 3 rotations, and 3 vibrations. C2v A1 A2 B1 B2

E C2 v(xz) v(yz)

1 1 1 1
9

1 1 -1 -1
-1

1 -1 1 -1
3

1 -1 -1 1
1

z Rz x, Ry y, Rx

x2, y2, z2 xy xz yz

Reducing reducible representation to irreducible representations!

# of irred. rep. of a given type

[ ] =
Order
21

# of operations in the class

Character of red. rep.

Character of irred. rep.

How many A1, A2, B1 and B2 are in ?

Reducing reducible representation to irreducible representations! # of irred. rep. of a given type # of A1 # of A2 # of B1 # of B2

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[ ] =
Order (191) + (1-11) + (131) + (111) 4 (191) + (1-11) + (13-1) + (11-1) 4 (191) + (1-1-1) + (131) + (11-1) 4 (191) + (1-1-1) + (13-1) + (111) 4

# of operations in the class

Character of red. rep.

Character of irred. rep.

= = = =

= 3 = 1 = 3 = 2
22

How many A1, A2, B1 and B2 are in ?

= 3A1 + A2 + 3B1 + 2B2

 Molecular Vibrations of Water

Irreducible rep. represents all molecular motions; = 3A1 + A2 + 3B1 + 2B2

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- 3 translations: A1 + B1 + B2 z x y directions! - 3 rotations: A2 + B1 + B2 Rz Ry Rx directions! - 3 vibrations: 2A1 + B1

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 MOs of Water
1. Determine the point group: C2v 2. Assign x, y, z coordinate to the atoms 3. Construct a reducible representation for two H atoms! = 2 0 2 0 4. Reduce red. ref. to irred. ref.; Symmetry-Adapted Linear Combination. = A1 + B1 5. Identify the AOs of the central atom with same symmetry 6. Combine the AOs of the central atom and others with matching symmetry and energy to form MOs! 7. # of AOs = # of MOs

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C2v A1 A2 B1 B2

C2

v(xz)

v(yz)

1 1 1 1
2

1 1 -1 -1
0

1 -1 1 -1
2

1 -1 -1 1
0

z Rz x, Ry y, Rx

x2, y2, z2 xy xz yz
24

 MOs of Water

Inorganic Chemistry

A1 (1/2) (Ha + Hb) B1 (1/2) (Ha - Hb)

25

 MOs of Water

Inorganic Chemistry

26

 MOs of Water
3

Inorganic Chemistry

1 4: 2Py Nonbonding 1: 2s + (Ha + Hb) Bonding 5: 2s - (Ha + Hb) Antibonding 2: 2Px + (Ha Hb) Bonding 3: 2Pz + (Ha + Hb) Slightly bonding 6: 2Px - (Ha Hb) Antibonding 27

 MOs of Water

Inorganic Chemistry

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 MOs of Water

Inorganic Chemistry

29