# Chem 59-250 Vibrational Spectroscopy

**A rough definition of spectroscopy is “the study of the interaction of matter
**

with energy (radiation in the electromagnetic spectrum).” A molecular

vibration is a periodic distortion of a molecule from its equilibrium geometry.

The energy required for a molecule to vibrate is quantized (not continuous)

and is generally in the infrared region of the electromagnetic spectrum.

r

e

= equilibrium distance between A and B

r

e

For a diatomic molecule (A-B), the bond between the two

atoms can be approximated by a spring that restores the

distance between A and B to its equilibrium value. The

bond can be assigned a force constant, k (in Nm

-1

; the

stronger the bond, the larger k) and the relationship

between the frequency of the vibration, e, is given by the

relationship:

D

AB

r

AB

0

D

AB

= energy required to dissociate into A and B atoms

e

µ

=

k

2t v

µ

c

k

=

or, more typically

where , c is the speed of light, v is the frequency in “wave

numbers” (cm

-1

) and µ is the reduced mass (in amu) of A

and B given by the equation:

µ =

×

+

m m

m m

A B

A B

Chem 59-250 Vibrational Spectroscopy

Molecule

v (cm

-1

) k (N/m)

µ (amu)

HF

3962 878 19/20

HCl 2886 477 35/36 or 37/38

HBr 2558 390 79/80 or 81/82

HI 2230 290 127/128

Cl

2

557 320 17.5

Br

2

321 246 39.5

CO 2143 1855 6.9

NO 1876 1548 7.5

N

2

2331 2240 7

2t v

µ

c

k

=

can be rearranged to solve for k (in N/m): k = ×

÷

589 10

5 2

. v µ

For a vibration to be active (observable) in an infrared (IR) spectrum, the vibration

must change the dipole moment of the molecule. (the vibrations for Cl

2

, Br

2

, and

N

2

will not be observed in an IR experiment)

For a vibration to be active in a Raman spectrum, the vibration must change the

polarizability of the molecule.

Chem 59-250

Vibrational Spectroscopy

For polyatomic molecules, the situation is more complicated because there are more

possible types of motion. Each set of possible atomic motions is known as a mode.

There are a total of 3N possible motions for a molecule containing N atoms because

each atom can move in one of the three orthogonal directions (i.e. in the x, y, or z

direction).

Translational

modes

Rotational

modes

A mode in which all the atoms are moving in the same

direction is called a translational mode because it is

equivalent to moving the molecule - there are three

translational modes for any molecule.

A mode in which the atoms move to rotate (change the

orientation) the molecule called a rotational mode - there

are three rotational modes for any non-linear molecule

and only two for linear molecules.

The other 3N-6 modes (or 3N-5 modes for a linear molecule) for a molecule

correspond to vibrations that we might be able to observe experimentally. We must

use symmetry to figure out what how many signals we expect to see and what atomic

motions contribute to the particular vibrational modes.

Chem 59-250 Vibrational Spectroscopy and Symmetry

1. Determine the point group of the molecule.

2. Determine the Reducible Representation, I

tot

, for all possible motions of

the atoms in the molecule.

3. Identify the Irreducible Representation that provides the Reducible

Representation.

4. Identify the representations corresponding to translation (3) and rotation

(2 if linear, 3 otherwise) of the molecule. Those that are left correspond

to the vibrational modes of the molecule.

5. Determine which of the vibrational modes will be visible in an IR or

Raman experiment.

We must use character tables to determine how many signals we will see

in a vibrational spectrum (IR or Raman) of a molecule. This process is

done a few easy steps that are similar to those used to determine the

bonding in molecules.

Chem 59-250

Example, the vibrational modes in water.

The point group is C

2v

so we must use the appropriate character table

for the reducible representation of all possible atomic motions, I

tot

. To

determine I

tot

we have to determine how each symmetry operation

affects the displacement of each atom the molecule – this is done by

placing vectors parallel to the x, y and z axes on each atom and

applying the symmetry operations. As with the bonds in the previous

examples, if an atom changes position, each of its vectors is given a

value of 0; if an atom stays in the same place, we have to determine

the effect of the symmetry operation of the signs of all three vectors.

The sum for the vectors on all atoms is placed into the reducible

representation.

Vibrational Spectroscopy and Symmetry

Make a drawing of the molecule and add in vectors

on each of the atoms. Make the vectors point in

the same direction as the x (shown in blue), the y

(shown in black) and the z (shown in red) axes.

We will treat all vectors at the same time when we

are analyzing for molecular motions.

H

O

H

H O H

top view

Chem 59-250

The E operation leaves everything where it is so all nine

vectors stay in the same place and the character is 9.

The C

2

operation moves both H atoms so we can ignore the

vectors on those atoms, but we have to look at the vectors on

the oxygen atom, because it is still in the same place. The

vector in the z direction does not change (+1) but the vectors

in the x, and y directions are reversed (-1 and -1) so the

character for C

2

is -1.

The o

v

(xz) operation leaves each atom where it was so we

have to look at the vectors on each atom. The vectors in the

z and x directions do not move (+3 and +3) but the vectors in

the y direction are reversed (-3) so the character is 3.

The o‟

v

(yz) operation moves both H atoms so we can ignore

the vectors on those atoms, but we have to look at the vectors

on the oxygen atom, because it is still in the same place. The

vectors in the z and y directions do not move (+1 and +1) but

the vectors in the x direction is reversed (-1) so the character

is 1.

C

2V

E C

2

o

v

(xz) o‟

v

(yz)

I

tot

9 -1 3 1

Example, the vibrational modes in water.

Vibrational Spectroscopy and Symmetry

H O H

C

2

H

O

H

H O H

H O H

H O H

o

v

(xz)

H O H

H O H

o‟

v

(yz)

z

y

x

Chem 59-250

C

2V

E C

2

o

v

(xz) o‟

v

(yz)

A

1

1 1 1 1 z x

2

,y

2

,z

2

A

2

1 1 -1 -1 R

z

xy

B

1

1 -1 1 -1 x, R

y

xz

B

2

1 -1 -1 1 y, R

x

yz

From the I

tot

and the character table, we can figure out the number and types of modes

using the same equation that we used for bonding:

( ) ( )

| |

n

1

order

# of operations in class (character of RR) character of X

X

= × ×

¿

( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )

| |

n

1

4

A

1

= + ÷ + + 1 9 1 1 1 1 1 3 1 1 1 1

This gives:

( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )

| |

n

1

4

B

1

= + ÷ ÷ + + ÷ 1 9 1 1 1 1 1 3 1 1 1 1

( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )

| |

n

1

4

B

2

= + ÷ ÷ + ÷ + 1 9 1 1 1 1 1 3 1 1 1 1

( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )

| |

n

1

4

A

2

= + ÷ + ÷ + ÷ 1 9 1 1 1 1 1 3 1 1 1 1

Which gives: 3 A

1

‟s, 1 A

2

, 3 B

1

‟s and 2 B

2

‟s or a total of 9 modes, which is what we

needed to find because water has three atoms so 3N = 3(3) =9.

Vibrational Spectroscopy and Symmetry

C

2V

E C

2

o

v

(xz) o‟

v

(yz)

I

tot

9 -1 3 1

Chem 59-250

Vibrational Spectroscopy and Symmetry

Now that we have found that the irreducible representation for I

tot

is (3A

1

+ A

2

+

3B

1

+ 2B

2

), the next step is to identify the translational and rotational modes - this

can be done by reading them off the character table! The three translational modes

have the symmetry of the functions x, y, and z (B

1

, B

2

, A

1

) and the three rotational

modes have the symmetry of the functions R

x

, R

y

and R

z

(B

2

, B

1

, A

2

).

Translational

modes

Rotational

modes

The other three modes (3(3)-6 = 3) that are left over for

water (2A

1

+ B

1

) are the vibrational modes that we might be

able to observe experimentally. Next we have to figure out if

we should expect to see these modes in an IR or Raman

vibrational spectrum.

C

2V

E C

2

o

v

(xz) o‟

v

(yz)

A

1

1 1 1 1 z x

2

,y

2

,z

2

A

2

1 1 -1 -1 R

z

xy

B

1

1 -1 1 -1 x, R

y

xz

B

2

1 -1 -1 1 y, R

x

yz

Chem 59-250

Remember that for a vibration to be observable in an IR

spectrum, the vibration must change the dipole moment of the

molecule. In the character table, representations that change

the dipole of the molecule are those that have the same

symmetry as translations. Since the irreducible representation

of the vibrational modes is (2A

1

+ B

1

) all three vibrations for

water will be IR active (in red) and we expect to see three

signals in the spectrum.

For a vibration to be active in a Raman spectrum, the vibration

must change the polarizability of the molecule. In the character

table, representations that change the polarizability of the

molecule are those that have the same symmetry as the second

order functions (with squared and multiplied variables). Thus all

three modes will also be Raman active (in blue) and we will see

three signals in the Raman spectrum.

Vibrational Spectroscopy and Symmetry

C

2V

E C

2

o

v

(xz) o‟

v

(yz)

A

1

1 1 1 1 z x

2

,y

2

,z

2

A

2

1 1 -1 -1 R

z

xy

B

1

1 -1 1 -1 x, R

y

xz

B

2

1 -1 -1 1 y, R

x

yz

The three vibrational

modes for water. Each

mode is listed with a v

(Greek letter „nu‟) and a

subscript and the energy

of the vibration is given

in parentheses. v

1

is

called the “symmetric

stretch”, v

3

is called the

“anti-symmetric stretch”

and v

2

is called the

“symmetric bend”.

the vibration must change the dipole moment of the molecule.9
NO
1876
2331
1548
2240
7. (the vibrations for Cl2.5
7
N2
For a vibration to be active (observable) in an infrared (IR) spectrum. and N2 will not be observed in an IR experiment) For a vibration to be active in a Raman spectrum.
.5 39. the vibration must change the polarizability of the molecule.89 10 5 2
(cm-1) 3962 k (N/m) 878 (amu) 19/20
Molecule HF
HCl
HBr HI Cl2 Br2 CO
2886
2558 2230 557 321 2143
477
390 290 320 246 1855
35/36 or 37/38
79/80 or 81/82 127/128 17.5 6. Br2.Chem 59-250 Vibrational Spectroscopy
2c k
can be rearranged to solve for k (in N/m): k 5.

We must use symmetry to figure out what how many signals we expect to see and what atomic motions contribute to the particular vibrational modes. the situation is more complicated because there are more possible types of motion.Chem 59-250
Vibrational Spectroscopy
For polyatomic molecules.e. There are a total of 3N possible motions for a molecule containing N atoms because each atom can move in one of the three orthogonal directions (i. Each set of possible atomic motions is known as a mode.there are three rotational modes for any non-linear molecule and only two for linear molecules.
Translational modes Rotational modes
The other 3N-6 modes (or 3N-5 modes for a linear molecule) for a molecule correspond to vibrations that we might be able to observe experimentally. or z direction).there are three translational modes for any molecule. A mode in which the atoms move to rotate (change the orientation) the molecule called a rotational mode .
A mode in which all the atoms are moving in the same direction is called a translational mode because it is equivalent to moving the molecule . y.
. in the x.

4. 3 otherwise) of the molecule. 1. Identify the representations corresponding to translation (3) and rotation (2 if linear. Those that are left correspond to the vibrational modes of the molecule.
. Determine the Reducible Representation. Determine which of the vibrational modes will be visible in an IR or Raman experiment. 2. This process is done a few easy steps that are similar to those used to determine the bonding in molecules.Chem 59-250 Vibrational Spectroscopy and Symmetry
We must use character tables to determine how many signals we will see in a vibrational spectrum (IR or Raman) of a molecule. for all possible motions of the atoms in the molecule. tot. 5. Identify the Irreducible Representation that provides the Reducible Representation. 3. Determine the point group of the molecule.

. the y (shown in black) and the z (shown in red) axes. Make the vectors point in the same direction as the x (shown in blue). We will treat all vectors at the same time when we are analyzing for molecular motions.
The point group is C2v so we must use the appropriate character table for the reducible representation of all possible atomic motions.
O H
H O
top view
H
H
Make a drawing of the molecule and add in vectors on each of the atoms. As with the bonds in the previous examples. tot. y and z axes on each atom and applying the symmetry operations. each of its vectors is given a value of 0. if an atom changes position.Chem 59-250 Vibrational Spectroscopy and Symmetry
Example. The sum for the vectors on all atoms is placed into the reducible representation. the vibrational modes in water. if an atom stays in the same place. To determine tot we have to determine how each symmetry operation affects the displacement of each atom the molecule – this is done by placing vectors parallel to the x. we have to determine the effect of the symmetry operation of the signs of all three vectors.

The vectors in the z and y directions do not move (+1 and +1) but the vectors in the x direction is reversed (-1) so the character is 1.Chem 59-250 Vibrational Spectroscopy and Symmetry
Example.
C2V tot E 9 C2 -1 v (xz) 3 1
v (xz)
H
O
H
H
O
H
‟v (yz)
‟v (yz)
H
O
H
. the vibrational modes in water. because it is still in the same place. The vector in the z direction does not change (+1) but the vectors in the x. but we have to look at the vectors on the oxygen atom. The vectors in the z and x directions do not move (+3 and +3) but the vectors in the y direction are reversed (-3) so the character is 3. The C2 operation moves both H atoms so we can ignore the vectors on those atoms. The ‟v (yz) operation moves both H atoms so we can ignore the vectors on those atoms. because it is still in the same place. and y directions are reversed (-1 and -1) so the character for C2 is -1.
The E operation leaves everything where it is so all nine vectors stay in the same place and the character is 9.
O H
H O
z y
H
H
x
C2
H
O H
O
H
The v (xz) operation leaves each atom where it was so we H have to look at the vectors on each atom. but we have to look at the vectors on the oxygen atom.

y2.z2 xy xz yz
From the tot and the character table.Chem 59-250 Vibrational Spectroscopy and Symmetry
C2V
tot C2V A1 A2 B1 B2 E 1 1 1 1
E
9 C2 1 1 -1 -1
C2
-1 v (xz) 1 -1 1 -1
v (xz)
3 ‟v (yz) 1 -1 -1 1
‟v (yz)
1
z Rz x. 1 A2. which is what we needed to find because water has three atoms so 3N = 3(3) =9. 3 B1‟s and 2 B2‟s or a total of 9 modes. Rx
x2. Ry y. we can figure out the number and types of modes using the same equation that we used for bonding:
nX 1 # of operations in class (character of RR) character of X order
This gives:
nA1
nA2
1 191 111 131 111 4
nB1
1 191 111 131 111 4
1 1 191 111 131 111 nB2 4 191 111 131 111 4
Which gives: 3 A1‟s.
.

A1) and the three rotational modes have the symmetry of the functions Rx. B2. and z (B1.
C2V E C2 v (xz) ‟v (yz)
A1
A2 B1 B2
1
1 1 1
1
1 -1 -1
1
-1 1 -1
1
-1 -1 1
z
Rz x.
.this can be done by reading them off the character table! The three translational modes have the symmetry of the functions x. A2). y.z2
xy xz yz
Translational Rotational modes modes
The other three modes (3(3)-6 = 3) that are left over for water (2A1 + B1) are the vibrational modes that we might be able to observe experimentally. Ry y.y2.Chem 59-250
Vibrational Spectroscopy and Symmetry
Now that we have found that the irreducible representation for tot is (3A1 + A2 + 3B1+ 2B2). Ry and Rz (B2. B1. Rx
x2. the next step is to identify the translational and rotational modes . Next we have to figure out if we should expect to see these modes in an IR or Raman vibrational spectrum.

In the character table. representations that change the dipole of the molecule are those that have the same symmetry as translations. Thus all three modes will also be Raman active (in blue) and we will see three signals in the Raman spectrum. Each mode is listed with a (Greek letter „nu‟) and a subscript and the energy of the vibration is given in parentheses.z2 xy xz yz
The three vibrational modes for water. the vibration must change the polarizability of the molecule.
For a vibration to be active in a Raman spectrum.y2.Chem 59-250
Vibrational Spectroscopy and Symmetry
Remember that for a vibration to be observable in an IR spectrum. In the character table. representations that change the polarizability of the molecule are those that have the same symmetry as the second order functions (with squared and multiplied variables). 3 is called the “anti-symmetric stretch” and 2 is called the “symmetric bend”. Ry y. Since the irreducible representation of the vibrational modes is (2A1 + B1) all three vibrations for water will be IR active (in red) and we expect to see three signals in the spectrum. 1 is called the “symmetric stretch”.
C2V A1 A2 B1 B2 E 1 1 1 1 C2 1 1 -1 -1 v (xz) 1 -1 1 -1 ‟v (yz) 1 -1 -1 1 z Rz x. Rx x2.
. the vibration must change the dipole moment of the molecule.

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