Important concepts in IR spectroscopy

Vibrations that result in change of dipole moment give rise to IR absorptions.

The oscillating electric field of the radiation couples with the molecular vibration
to cause an alternating electric field produced by the changing dipole.

Absorption bands in vibration spectra appear as broad bands (not a single

energy) if the rotational states of the molecules are not resolved as it is usually
the case in liquid or solid phases.

An IR spectrum is characteristic of an entire molecule and is as unique as a

fingerprint (molecular fingerprint). Many localized vibrations help to
identify functional groups.

Band intensities are expressed as either transmission (T) or absorption (A)

A = log10(1/T)

In addition to fundamental transitions, IR spectra can contain overtone bands,

due to excitation into higher vibrational states, and combination bands, due
to coupling of two or several group vibrations. Group vibrations can couple if
their frequencies are similar and they share a common atom. A special case of
coupling occurs when a fundamental vibration couples with an overtone or
combination vibration. This phenomenon is known as Fermi resonance.

Types of Molecular Vibrations

Stretching or bonding vibrations () alter the bond lengths;

Bending or deformation vibrations alter the bond angles, while the

bond lengths remain unchanged; They can be subdivided into in-plane
() and out-of-plane modes (); These modes are often referred to as
twisting, wagging, and rocking vibration of a fragment;

Torsional vibrations involve an alternation of the torsion angle;

A further division into symmetric (s), antisymmetric (as), and

degenerated (e) vibrations is possible.
in-plane out-of-plane in-plane

IR and molecular symmetry

Every atom has a translational freedom of 3 because it can move in

one of the three orthogonal directions (i.e. in the x, y, or z
direction). There are a total of 3N possible motions for a molecule
containing N atoms and each set of possible atomic motions is
known as a mode.
Linear molecules, such as CO2, have 3N-5 vibrational modes
because 3 of all the modes result in a translation and 2 in a rotation.

1285 cm-1
(s) C=O
IR inactive, Raman active

2349 cm-1 (as) C=O

IR active, Raman active

(s) O=C=O
666 cm-1 IR active, degenerated

1
 Bent molecules, such as H2O, have 3N-6 vibrational modes because 3 of all the
modes result in a translation and 3 in a rotation.

(s) O-H
3657 cm-1 IR active
(as) O-H
3756 cm-1 IR active

(s) H-O-H
1595 cm-1 IR active, degenerated

All IR absorptions result not only in a vibrational excitation but also in transitions
between different rotational states. Those rotational transitions can be resolved in
gas phase IR spectroscopy. Rotational spectroscopy specifically measures
transitions between rotational states and involves microwave radiation. It is an
important method in gas phase chemistry.

59-250, notes 6, Macdonald

Vibrational Spectroscopy and Symmetry
Example, the vibrational modes of water.
z y
The E operation leaves everything where it is so all nine O
vectors stay in the same place and the character is 9. H H x

The C2 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
H O H
C2
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 H O H
character for C2 is -1.
The v (xz) operation leaves each atom where it was so we H O H
have to look at the vectors on each atom. The vectors in the
v (xz)
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. H O H
The 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
H O H
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 v (yz)
is 1.
C2V E C2 v (xz) v (yz)
H O H
tot 9 -1 3 1

Vibrational Spectroscopy and Symmetry

C2V E C2 v (xz) v (yz)
tot 9 -1 3 1

C2V E C2 v (xz) v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

From the tot and the character table, we can figure out the number and types of modes
using the same equation that we used for bonding:
1
nX =
order
[
(# of operations in class) (character of RR) (character of X) ]
This gives:
1 1
nA1 =
4
[(1)(9)(1) + (1)(1)(1) + (1)(3)(1) + (1)(1)(1) ] nB1 =
4
[(1)(9)(1) + (1)(1)(1) + (1)(3)(1) + (1)(1)(1) ]
1
nA 2 =
1
4
[ ] [
(1)(9)(1) + (1)(1)(1) + (1)(3)(1) + (1)(1)(1) nB2 = 4 (1)(9)(1) + (1)(1)(1) + (1)(3)(1) + (1)(1)(1) ]
Which gives: 3 A1s, 1 A2, 3 B1s and 2 B2s or a total of 9 modes, which is what we
needed to find because water has three atoms so 3N = 3(3) =9.

2
 An IR active vibrational
mode must result in a
change of dipole
moment of the absorbing
group;

The requirement for a

Raman active vibrational
mode is a change in
polarizability of the
absorbing group;

Almost every chemical

bond between different
elements has a dipole
moment but dipole
moments of a
functional group or
molecule might cancel
out due to symmetry!

Stretching and Bending vibrations of CH2

+ +

-
(as) 2926 cm-1 (s) 2853 cm-1 (in-plane) 1465 cm-1 (out-of-plane)
1350-1150 cm-1

+ -
In-plane bend
Out-of plane
or rocking
bend or twist
750-710 cm-1
1350-1150 cm-1

a 1
CH3

b H3
2H
c
8H d
e H4
i
k 5
f CH3
7H h O
g

OH 6

2-methoxyphenol (Guaiacol)

trans-methylstyrene

3
 IR of Normal Alkanes
C-C
C-H Stretch 1200-800 (weak)
CH3 (as) 2962 C-H Bend C-C bend
CH3 (s) 2872 CH2 (s) 1467 below 500
CH2(as) 2924 CH3 (as) 1450 C-H twist
CH2(s) 2853 CH3(s) 1378 CH 1350-1150 C-H Rock
2
(weak) CH2 721

dodecane

IR of Alkenes
C=C Stretch in simple alkenes 1670-1640
C=C in conjugated alkenes near 1650 and 1600 (why lower?)

C-H bend (aliphatic &

C-H bend
C-H stretch alkene in-plane)
(out-of-plane)

C=C
1640 (s) w

=C-Hstretch C=C
1598(as) s isoprene

IR of Alkynes

C-H stretch
C-H bend
CC stretch C-H bend 630
C-H stretch 2119 overtone 1250
3310

1-hexyne

4
 Aromatics
Prominent (strong) absorptions:

C-H stretch 3100-3000 cm-1

in-plane C-H bend 1300-1000 cm-1

out of plane C-H bend 900-675 cm-1

(characteristic for substitution pattern)

C=C ring stretches 1600-1585 and 1500-1400 cm-1

out of plane C=C bend 450-400 cm-1

Overtone and Combination bands 2000-1650 cm-1

combination bands

C=C ring

out of plane C-H bend

Aromatic overtone and combination bands