10 5

A Second Application of Symmetry
Chapter 4
Monday, October 5, 2015

Using Symmetry: Vibrational Spectroscopy
IR and Raman spectra can be interpreted using symmetry.
• For nonlinear molecules, the number of vibrational modes

is 3N - 6, where N is the number of atoms and 3N the number of
degrees of freedom
y
• Consider N2O4, which is D2h x
• Each atom can move in three dimensions

• If all atoms move the same amount in the same direction the molecule moves,
which is a translation, not a vibration (accounts for three degrees of freedom)
• Molecule can also rotate around the three orthogonal axes (which accounts
for three more degrees of freedom)
• So for N2O4 we predict that there will be 3N - 6 = 12 vibrational
modes
We can use character tables to determine the symmetry of all 18
motions and then assign them to translation, rotation, or vibration.
We can also tell which vibrations are IR or Raman active.
Procedure:
1. Assign x,y,z coordinates to each atom.
y
z x
2. Determine how each axis transforms for every class of

symmetry operation in the group.
• If an atom moves, the character for all of its axes is 0
• If an atom is stationary and the axis direction is unchanged, its character is 1
• If an atom is stationary and the axis direction is reversed, its character is -1
3. Sum the characters in each class to determine the reducible

representation Γ
D2h E C2(z) C2(y) C2(x) i σ(xy) σ(xz) σ(yz)
Γ 18 0 0 -2 0 6 2 0
E: all 18 axes unchanged  χ = 18

C2(z): all atoms move χ=0 y
C2(y): all atoms move χ=0 z x
C2(x): oxygens move
N’s x unchanged
N’s y,z reversed  χ = -2
i: all atoms move χ=0 Γ is the reducible
σ(xy): z axes reversed representation for all
x,y axes unchanged  χ = 6 motions of N2O4
σ(xz): oxygens move
N’s x,z unchanged
N’s y reversed χ=2
σ(yz): all atoms move χ=0
D2h E C2(z) C2(y) C2(x) i σ(xy) σ(xz) σ(yz)
Γ 18 0 0 -2 0 6 2 0
4. Now reduce Γ to its irreducible components using the character

table and the following property of groups:
# of irreducible # of character of character of
representations = operations × reducible × irreducible
of a given type in the class representation representation
# Ag = 1/8*[18+0+0-2+0+6+2+0] = 3
# B1g = 1/8*[18+0+0+2+0+6-2+0] = 3
# B2g = 1/8*[18+0+0+2+0-6+2+0] = 2
# B3g = 1/8*[18+0+0-2+0-6-2+0] = 1
# Au = 1/8*[18+0+0-2+0-6-2+0] = 1
# B1u = 1/8*[18+0+0+2+0-6+2+0] = 2
# B2u = 1/8*[18+0+0+2+0+6-2+0] = 3
# B3u = 1/8*[18+0+0-2+0+6+2+0] = 3
So, Γ = 3Ag + 3B1g + 2B2g + B3g + Au + 2B1u + 3B2u + 3B3u
The reducible representation is the sum of 18 irreducible reps:

Γ = 3Ag + 3B1g + 2B2g + B3g + Au + 2B1u + 3B2u + 3B3u
5. Now use the character table to subtract the translations and

rotations, leaving the representations corresponding to the
vibrations.
Translations (x,y,z) = B1u + B2u + B3u

Rotations (Rx,Ry,Rz) = B1g + B2g + B3g
Vibrational modes (all that remain) =
3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u
These are the symmetries of the

12 vibrational modes of N2O4
Let’s consider the vibrational modes of N2O4 in a little more detail.
Vibrations = 3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u
Using the table, we can guess what these modes might look like.
e.g., the three Ag modes are totally symmetric:
NO2 sym. stretch NO2 sym. bend N-N stretch
the Au mode is symmetric w.r.t C2 but antisymmetric w.r.t. σ and i:
torsion
The character table tells us whether the vibrational modes are IR
active and/or Raman active.
To be IR active (allowed), the vibration must change the dipole

moment of the molecule.
• Only irreducible representations with x,y,z symmetry do this
N2O4 vibrations = 3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u

IR active: B1u + 2B2u + 2B3u
The character table tells us whether the vibrational modes are IR
active and/or Raman active.
To be Raman active (allowed), the vibration must change the

polarizability of the molecule.
• Only irreducible representations that transform like the
binary products of x,y, and z (i.e., xy, xz, yz, x2, y2, z2 or their
linear combinations) do this
N2O4 vibrations = 3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u

Raman active: 3Ag + 2B1g + B2g
*Note that the Au mode is

IR and Raman silent.
Using Symmetry: Selected Vibrational Modes
We may be interested in the vibrations of specific groups in a
molecule rather than all possible motions of the molecule.
e.g., C-O stretching in metal carbonyl complexes
In this case, we can create reducible representations of the bond
vectors of interest, determine their irreducible components, and find
the active modes.
Example: can we use IR/Raman spectroscopy to distinguish

between fac-ML3(CO)3 and mer-ML3(CO)3 isomers?
CO
Cl OC Cl
OC CO OC CO
Cl
facial meridional
C3v C2v
Let’s create reducible representations of the C-O bonds in each
molecule:
O≡C
Cl
Cl
χ = 1 if unchanged facial
χ = 0 if changed C3v
C3v E 2C3 3σv
Γ 3 0 1
Reduce to irreducible representations: # A1 = 1/6*[3+0+3] = 1

# A2 = 1/6*[3+0-3] = 0
# E = 1/6*[6+0+0] = 1
So, Γ = A1 + E
molecule:
O≡C
Cl
Cl
facial
C3v
Γ = A1 + E
IR active (x,y,z): A1 and E (2 peaks predicted)
Raman active (quadratic): A1 and E (2 peaks predicted)
 The fac isomer is expected to have 2 peaks in both its IR and

Raman spectra.
molecule:
Cl
χ = 1 if unchanged
meridional
χ = 0 if changed
C2v
C2v E C2(z) σv(xz) σv(yz)
Γ 3 1 3 1
# A1 = 1/4*[3+1+3+1] = 2
Reduce to irreducible representations: # A2 = 1/4*[3+1-3-1] = 0
# B1 = 1/4*[3-1+3-1] = 1
# B2 = 1/4*[3-1-3+1] = 0
So, Γ = 2A1 + B1
molecule:
Cl
meridional
C2v
Γ = 2A1 + B1
IR active (x,y,z): A1 and B1 (3 peaks predicted)
Raman active (quadratic): A1 and B1 (3 peaks predicted)
 The mer isomer is expected to have 3 peaks in both its IR

and Raman spectra.
Summary
Group theory can tell us which molecules are chiral, possess dipole
moments, possess chemically identical groups, and other symmetry-
related properties
We can use group theory to determine the vibrational modes of

molecules. Procedure:
• Determine point group of molecule
• Determine reducible representation for vectors of interest
• Reduce this representation to its irreducible components (modes)
• If desired, assign the modes to the different motions (rotations,
translations, stretches, bends, wags, twists, etc.)
• If desired, read off which modes are IR/Raman active
To dig deeper, check out: Cotton, F. A. Chemical Applications of Group Theory.

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A Second Application of Symmetry

Monday, October 5, 2015

• For nonlinear molecules, the number of vibrational modes

• Consider N2O4, which is D2h x

• Each atom can move in three dimensions

2. Determine how each axis transforms for every class of

3. Sum the characters in each class to determine the reducible

E: all 18 axes unchanged  χ = 18

4. Now reduce Γ to its irreducible components using the character

The reducible representation is the sum of 18 irreducible reps:

5. Now use the character table to subtract the translations and

Translations (x,y,z) = B1u + B2u + B3u

These are the symmetries of the

Vibrations = 3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u

NO2 sym. stretch NO2 sym. bend N-N stretch

the Au mode is symmetric w.r.t C2 but antisymmetric w.r.t. σ and i:

To be IR active (allowed), the vibration must change the dipole

N2O4 vibrations = 3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u

To be Raman active (allowed), the vibration must change the

N2O4 vibrations = 3Ag + 2B1g + B2g + Au + B1u + 2B2u + 2B3u

*Note that the Au mode is

Example: can we use IR/Raman spectroscopy to distinguish

C3v E 2C3 3σv

Reduce to irreducible representations: # A1 = 1/6*[3+0+3] = 1

 The fac isomer is expected to have 2 peaks in both its IR and

C2v E C2(z) σv(xz) σv(yz)

 The mer isomer is expected to have 3 peaks in both its IR

We can use group theory to determine the vibrational modes of

To dig deeper, check out: Cotton, F. A. Chemical Applications of Group Theory.

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