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I.
Matrices
A.
Why Matrices? The matrix representations of the point groups operations will
generate a character table. We can use this table to predict properties.
B.
3 2
7 1 or 3 4 2 5
Multiplying Matrices
a) The number of columns of matrix #1 must = number of rows of matrix #2
b) Fill in answer matrix from left to right and top to bottom
c) The first answer number comes from the sum of [(row 1 elements of matrix
#1) X (column 1 elements of matrix #2)]
d) The answer matrix has same number of rows as matrix #1
The answer matrix has same number of columns as matrix #2
1 5 7 3 7 20 3 40 27 43
2 6 4 8 14 24 6 48 38 54
e)
Relevant example:
1 0 0
1 2 3 0 1 0 1 2 3
0 0 1
f)
II.
Exercise 4-4
2)
3)
x' ? ? ?
y' ? ? ?
z' ? ? ?
x
y
z
transformation
matrix
4)
E Transformation Matrix
a. x,y,z x,y,z
b. What matrix times x,y,z doesnt change anything?
1 0 0
0 1 0
0 0 1
x
y
z
x
y
z
E Transformation Matrix
5)
C2 Transformation Matrix
a.
b.
6)
0
0
1 0
0 1
x - x
y - y
z z
7)
x,y,z x,-y,z
Correct matrix is:
1 0 0
0 1 0
0 0 1
x
y
z
x
- y
z
x,y,z -x,y,z
Correct matrix is:
1 0 0 x - x
0 1 0 y y
0 0 1 z z
8)
These 4 matrices are the Matrix Representation of the C2v point group
a.
b.
1 0 0 1 0 0 1 0 0
0 1 0 0 1 0 0 1 0
0 0 1 0 0 1 0 0 1
B.
a)
C2
v(xz)
v(yz)
-1
2)
1
0
1
0
E
c.
d.
1
0
1
0
v(xz)
C2
v(yz)
When you do this, the x,y, and z axes can be treated independently
i. Positions 1,1 always describe x-axis
ii. Positions 2,2 always describe y-axis
iii. Positions 3,3 always describe z-axis
Generate a partial character table from this treatment
E
C2
v(xz)
v(yz)
x
Irreducible
Representations y
z
-1
-1
-1
-1
Reducible Repr.
-1
Axis used
C2v
C2
v(xz)
v(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
3)
4)
B.
2)
C.
Though more complex, the C3v Character Table can be generated similarly to
that of the C2v group
b)
c)
Subscripts
i. 1 if symmetric to perpendicular C2 axis (or v)
ii. 2 if antisymmetric to perpendicular C2 axis (or v)
iii. g if symmetric to i
iv. u if antisymmetric to i
Primes
i. if symmetric to h
ii.
if antisymmetric to h
Chiral Molecules
1) Molecules not superimposable with their mirror images are called chiral
or dissymetric
2) They may still have some symmetry operations: E, Cn
3)
B.
Molecular Vibrations
1. To use symmetry, we must assign axes
to each atom of the molecule
a. The z-axis is usually the Cn axis
b. The x-axis is in the molecular plane
c. The y-axis is perpendicular to the molecular plane
2.
3.
We will use group theory to determine the symmetry of all nine motions
and then assign them to translation, rotation, and vibration
a)
C2v
C2
v(xz)
v(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
b)
C2v
c)
C2
v(xz)
v(yz)
9
-1
3
1
Reduce the reducible representation to its irreducible components
The number of
irreducible representations 1
order
of a given type
number of operations
in
the
class
character of the
reducible
representa
tion
character of the
irreducibl
e
representa
tion
d)
i. nA1 = [(1x9x1)+(1x-1x1)+(1x3x1)+(1x1x1)] = 3 A1
ii. nA2 = [(1x9x1)+(1x-1x1)+(1x3x-1)+(1x1x-1)] = 1 A2
iii. nB1 = [(1x9x1)+(1x-1x-1)+(1x3x1)+(1x-1x1)] = 3 B1
iv. nB2 = [(1x9x1)+(1x-1x-1)+(1x3x-1)+(1x1x1)] = 2 B2
All motions of water match 3A1 + A2 + 3B1 + 2B2
e)
f)
g)
C.
4)
Symmetry and IR
a. IR only sees a vibration if the vibration changes the molecules dipole
b. Motion along the x, y, z axes creates a changed dipole
a. Infrared Active vibrations match up with x, y, z on character table
b. Infrared Inactive vibrations dont
c. For water, all three vibrations are infrared active
5)
c)
C2v
d)
C2
v(xz)
v(yz)
2
0
2
0
2 possible vibrations from reduction formula: A1 + B1 (see both)
2)
c.
d.