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1

Single Atom

Vibration- Atoms of a molecule changing their relative positions

without changing the position of the molecular center of mass.

No Vibartion

“It takes two to vibrate”

No Rotation

A point cannot rotate

Translation

Can move in x, y, and/or z

2

0 Vibrations

Diatomic Molecule

Translation 6 DOF

- 3 Translation

- 2 Rotation

1 Vibration

Rotation

# of Vibrations = 3N-53

Linear Triatomic Molecule

9 DOF

- 3 Translation

- 2 Rotation

4 Vibration

# of Vibrations = 3N-5

Argon (1% of the atmosphere)-

4

3 DOF, 0 Vibrations

Nonlinear Triatomic Molecule

3 Translation

3 Rotation

Linear non-linear

5

Nonlinear Triatomic Molecule

Transz Rz 9 DOF

- 3 Translation

Transy - 3 Rotation

Rx 3 Vibration

# of Vibrations = 3N-6 6

Nonlinear Triatomic Molecule

9 DOF

- 3 Translation

- 3 Rotation

3 Vibration

# of Vibrations = 3N-6 7

Molecular Vibrations

Atoms of a molecule changing their relative positions without

changing the position of the molecular center of mass.

Center of Mass

In terms of the molecular geometry

these vibrations amount to

continuously changing bond lengths

and bond angles. Reduced Mass

8

Molecular Vibrations

Hooke’s Law

k = force constant

x = distance

Assumes-

It takes the same energy to stretch

the bond as to compress it.

9

Molecular Vibrations

Vibration Frequency (n)

Related to:

Stiffness of the bond (k).

10

Molecular Vibrations

Classical Spring

Quantum Behavior

Especially at low energies. 11

6 Types of Vibrational Modes

Symmetric Stretch Assymmetric Stretch Wagging

12

Vibrations and Group Theory

What kind of information can be deduced about the internal

motion of the molecule from its point-group symmetry?

an irreducible representation of the point group

of the molecule.

2) Assign the symmetry of known vibrations.

3) What does the vibration look like?

4) Find if a vibrational mode is IR or Raman Active.

13

1) Finding Vibrational Modes

1. Assign a point group

2. Choose basis function (three Cartesian

coordinates or a specific bond)

3. Apply operations

-if the basis stays the same = +1

-if the basis is reversed = -1

-if it is a more complicated change = 0

4. Generate a reducible representation

5. Reduce to Irreducible Representation

6. Subtract Translational and Rotational Motion

14

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

Atom 1: x1 = 1 Atom: 1 2 3

y1 = 1 E: 3+3+3 = 9

z1 = 1

Atom 2: x2 = 1

E y2 = 1

z2 = 1

Atom 3: x3 = 1

y3 = 1

z3 = 1 15

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

Atom 1: x1 = 0 Atom: 1 2 3

y1 = 0 E: 3+3+3 = 9

z1 = 0

Atom 2: x2 = -1 C2: 0 + -1 + 0 = -1

C2 y2 = -1

z2 = 1

Atom 3: x3 = 0

y3 = 0

z3 = 0 16

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

Atom 1: x1 = 0 Atom: 1 2 3

y1 = 0 E: 3+3+3 = 9

z1 = 0

Atom 2: x2 = 1 C2: 0 + -1 + 0 = -1

sxz y2 = -1

z2 = 1 sxz: 0 + 1 + 0 = 1

Atom 3: x3 = 0

y3 = 0

z3 = 0 17

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

Atom 1: x1 = -1 Atom: 1 2 3

y1 = 1 E: 3+3+3 = 9

z1 = 1

Atom 2: x2 = -1 C2: 0 + -1 + 0 = -1

syz y2 = 1

z2 = 1 sxz: 0 + 1 + 0 = 1

Atom 3: x3 = -1

y3 = 1 syz: 1 + 1 + 1 = 3

z3 = 1 18

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

4. Generate a reducible representation

Atom: 1 2 3

E: 3+3+3 = 9

C2: 0 + -1 + 0 = -1

G 9 -1 1 3

sxz: 0 + 1 + 0 = 1

syz: 1 + 1 + 1 = 3

19

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

4. Generate a reducible representation

5. Reduce to Irreducible Representation

G 9 -1 1 3

Example: H2O

Decomposition/Reduction Formula

order (h)

h=1+1+1+1=4

G 9 -1 1 3

1 12

aA1 =

4

[ ]

(1)(9)(1) + (1)(-1)(1) + (1)(1)(1) + (1)(3)(1) =

4

= 3

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

3 atoms x 3 DOF = 9 DOF

4. Generate a reducible representation 3N-6 = 3 Vibrations

5. Reduce to Irreducible Representation

6. Subtract Rot. and Trans.

Trans = A1 + B1 + B2

Rot = A2 + B1 + B2

Vib = 2A1 + B2 22

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: x1-3, y1-3 and z1-3

-if it is a more complicated change = 0

4. Generate a reducible representation Vibration = 2A1 + B2

5. Reduce to Irreducible Representation

6. Subtract Rot. and Trans.

23

Example: H2O

1. Start with a drawing of a molecule

2. Draw arrows

C2v point group

3. Use the Character Table Basis: x1-3, y1-3 and z1-3

4. Predict a physically observable phenomenon

Vibrations = 2A1 + B2

B2

A1 All three are IR active

but that is not always

the case.

A1

24

Vibrations and Group Theory

1) Find number/symmetry of vibrational modes.

2) Assign the symmetry of known vibrations.

3) What does the vibration look like?

4) Find if a vibrational mode is IR or Raman Active.

25

2) Assign the Symmetry of a Known Vibrations

Stretch Stretch Bend

Vibrations = 2A1 + B2

Bend

1. Assign a point group

2. Choose basis function (stretch or bend)

3. Apply operations

-if the basis stays the same = +1 Stretch

-if the basis is reversed = -1

-if it is a more complicated change = 0

4. Generate a reducible representation

5. Reduce to Irreducible Representation 26

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: Bend angle

-if it is a more complicated change = 0

E

E: 1

C2

C2: 1

sxz

sxz: 1

syz

syz: 1 27

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: Bend angle

-if it is a more complicated change = 0

4. Generate a reducible representation

5. Reduce to Irreducible Representation

G 1 1 1 1

2) Assign the Symmetry of a Known Vibrations

Stretch Stretch Bend

A1

Vibrations = A1 + B2

1. Assign a point group

2. Choose basis function (stretch)

3. Apply operations

-if the basis stays the same = +1 Stretch

-if the basis is reversed = -1

-if it is a more complicated change = 0

4. Generate a reducible representation

5. Reduce to Irreducible Representation 29

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: OH stretch

-if it is a more complicated change = 0

E

E: 2

C2

C2: 0

sxz

sxz: 0

syz

syz: 2 30

Example: H2O

1. Assign a point group

2. Choose basis function

3. Apply operations

-if the basis stays the same = +1 C2v point group

-if the basis is reversed = -1 Basis: OH stretch

-if it is a more complicated change = 0

4. Generate a reducible representation

5. Reduce to Irreducible Representation

G 2 0 0 2

Example: H2O

Decomposition/Reduction Formula

order (h)

h=1+1+1+1=4

G 2 0 0 2

1 4

aA1 =

4

[ ]

(1)(2)(1) + (1)(0)(1) + (1)(0)(1) + (1)(2)(1) =

4

= 1

1 4

aB2 = [ ]

(1)(2)(1) + (1)(0)(-1) + (1)(0)(-1) + (1)(2)(1) = = 1

4 4

G = A1 + B2 32

2) Assign the Symmetry of a Known Vibrations

Stretch Stretch Bend

A1

Vibrations = A1 + B2

By Inspection By Projection Operator

33

Vibrations and Group Theory

1) Find number/symmetry of vibrational modes.

2) Assign the symmetry of known vibrations.

3) What does the vibration look like?

4) Find if a vibrational mode is IR or Raman Active.

34

3) What does the vibration look like?

By Inspection

G = A1 + B2

G 1 1 1 1 G 1 -1 -1 1

A1 B2

35

3) What does the vibration look like?

Projection Operator

2. Choose non-symmetry basis (Dr1)

3. Choose a irreducible representation (A1 or B2)

4. Apply Equation

- Use operations to find new non-symmetry basis (Dr1)

- Multiply by characters in the irreducible representation

5. Apply answer to structure

36

3) What does the vibration look like?

Projection Operator

1. Assign a point group

2. Choose non-symmetry basis (Dr1)

3. Choose a irreducible representation (A1) C2v point group

4. Apply Equation Basis: Dr1

- Use operations to find new non-symmetry basis (Dr1)

- Multiply by characters in the irreducible representation For A1

E

C2

sxz

syz

37

3) What does the vibration look like?

Projection Operator

1. Assign a point group

2. Choose non-symmetry basis (Dr1)

3. Choose a irreducible representation (A1) C2v point group

4. Apply Equation Basis: Dr1

- Use operations to find new non-symmetry basis (Dr1)

- Multiply by characters in the irreducible representation For A1

E

C2

sxz

syz

38

3) What does the vibration look like?

Projection Operator

1. Assign a point group

2. Choose non-symmetry basis (Dr1)

3. Choose a irreducible representation (B2) C2v point group

4. Apply Equation Basis: Dr1

- Use operations to find new non-symmetry basis (Dr1)

- Multiply by characters in the irreducible representation For B2

E

C2

sxz

syz

39

3) What does the vibration look like?

Projection Operator

1. Assign a point group

2. Choose non-symmetry basis (Dr1)

3. Choose a irreducible representation (B2) C2v point group

4. Apply Equation Basis: Dr1

- Use operations to find new non-symmetry basis (Dr1)

- Multiply by characters in the irreducible representation

5. Apply answer to structure

A1 B2

40

3) What does the vibration look like?

A1 A1 B2

B2 + = vibrational modes of

A1 Point Group the molecule

Does not tell us IR or Raman active!

41

Vibrations of C60

1) Find number/symmetry of vibrational modes.

2) Assign the symmetry of known vibrations.

3) What does the vibration look like?

4) Find if a vibrational mode is IR or Raman Active.

42

Vibrations of C60

43

Vibrations of C60

44

Vibrations of C60

45

Vibrations and Group Theory

1) Find number/symmetry of vibrational modes.

2) Assign the symmetry of known vibrations.

3) What does the vibration look like?

4) Find if a vibrational mode is IR or Raman Active.

Next ppt!

46

Side note: A Heroic Feat in IR Spectroscopy

47

Kincaid et al. J . Phys. Chem. 1988, 92, 5628.

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