Class 02 Advanced Inorganic Chemistry: Symmetry & Group Theory
Class 02 Advanced Inorganic Chemistry: Symmetry & Group Theory
Class 02 Advanced Inorganic Chemistry: Symmetry & Group Theory
Inorganic Chemistry
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
Inorganic Chemistry
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
Inorganic Chemistry
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
Inorganic Chemistry
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
Inorganic Chemistry
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
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
Inorganic Chemistry
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
Inorganic Chemistry
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
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
Inorganic Chemistry
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
Inorganic Chemistry
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.
9
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.
Inorganic Chemistry
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
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
Inorganic Chemistry
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
12
Area I
Inorganic Chemistry
13
Area I
Inorganic Chemistry
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
Area I
Inorganic Chemistry
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
Inorganic Chemistry
- 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
Inorganic Chemistry
y z x
0 0 0
Ha Hb
y z x y z
0 0 0
Ha Hb
17
0 0
Character () = 9
Inorganic Chemistry
y z x
0 0 0
Ha Hb
y z x y z
0 0 0
Ha Hb
18
0 0
Character () = -1
Inorganic Chemistry
y z x
0 0 0
Ha Hb
y z x y z
0 0 0
Ha Hb
19
0 0
Character () = 3
Inorganic Chemistry
y z x
0 0 0
Ha Hb
y z x y z
0 0 0
Ha Hb
20
0 0
Character () = 1
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
[
]
=
Order
21
Inorganic Chemistry
[
]
=
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
= = = =
= 3 = 1 = 3 = 2
22
Inorganic Chemistry
23
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
Inorganic Chemistry
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
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
28
MOs of Water
Inorganic Chemistry
29