Fall 2005

Chapter 2: IR Spectroscopy
Spectroscopic Process
IR Absorption Process
Uses of IR
Covalent bonds
Vibrational Modes
Absorption Trends

CHMBD 449 Organic Spectral

Analysis
1

IR Spectroscopy
I.

Introduction
F. The IR Spectrum
4. The intensity of an IR band is affected by two primary factors:
Whether the vibration is one of stretching or bending
Electronegativity difference of the atoms involved in the
bond:
For both effects, the greater the change in dipole moment
in a given vibration or bend, the larger the peak
The greater the difference in electronegativity between the
atoms involved in bonding, the larger the dipole moment
Typically, stretching will change dipole moment more than
bending
5.

It is important to make note of peak intensities to show the

effect of these factors:
Strong (s) peak is tall, transmittance is low
Medium (m) peak is mid-height
Weak (w) peak is short, transmittance is high
2
* Broad (br) if the Gaussian distribution is abnormally

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
We have learned:
That IR radiation can couple with the vibration of
covalent bonds, where that particular vibration causes a
change in dipole moment

The IR spectrometer irradiates a sample with a continuum

of IR radiation; those photons that can couple with the
vibrating bond elevate it to the next higher vibrational
energy level (increase in A)

When the bond relaxes back to the 0 state, a photon of the

same is emitted and detected by the spectrometer; the
spectrometer reports this information as a spectral band
centered at the of the coupling

The position of the spectral band is dependent on bond

strength and atomic size

The intensity of the peak results from the efficiency of the

3
coupling; e.g. vibrations that have a large change in dipole

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
Remember, most interesting molecules are not diatomic, and
mechanical or electronic factors in the rest of the structure may
effect an IR band
From a molecular point of view (discounting phase, temperature or
other experimental effects) there are 10 factors that contribute to the
position, intensity and appearance of IR bands
1. Symmetry
2. Mechanical Coupling
3. Fermi Resonance
4. Hydrogen Bonding
5. Ring Strain
6. Electronic Effects
7. Constitutional Isomerism
8. Stereoisomerism
9. Conformational Isomerism
10. Tautomerism (Dynamic Isomerism)
4

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
1. Symmetry H2O
For a particular vibration to be IR active there must be a
change in dipole moment during the course of the
particular vibration
For example, the carbonyl vibration causes a large shift in
dipole moment, and therefore an intense band on the IR
spectrum
-

+
C

vibration

+
C

For a symmetrical acetylene, it is clear that there is no

permanent dipole at any

point in the vibration of the CC
vibration
bond.C NoCIR band appears on the spectrum
C
C
5

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
1. Symmetry H2O
Most organic molecules are fortunately asymmetric, and
bands are observed for most molecular vibration
The symmetry problem occurs most often in small, simple
symmetric and pseudo-symmetric alkenes and alkynes
H3C

CH3
C

H3C

H2C
C

H3C

CH3

H2
C

CH3

H3C

H3C

symmetric

CH3

psuedo-symmetric

H3C

CH3

CH3

Since symmetry elements cancel the presence of bonds

where no dipole is generated, the spectra are greatly
simplified
6

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
1. Symmetry H2O
Symmetry also effects the strength of a particular band
The symmetry problem occurs most often in small, simple
symmetric and pseudo-symmetric alkenes and alkynes
H3C

CH3
C

H3C

H2C
C

H3C

CH3

H3C

H2
C

CH3

H3C

H3C

symmetric

CH3

psuedo-symmetric

CH3

CH3

Since symmetry elements cancel the presence of bonds

where no dipole is generated, the spectra are greatly
simplified
7

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
2. Mechanical Coupling
In a multi-atomic molecule, no vibration occurs without
affecting the adjoining bonds

This induces mixing and redistribution of energy states,

yielding new energy levels, one being higher and one lower
in frequency

Coupling parts must be approximate in E for maximum

interaction to occur (i.e. C-C and C-N are similar, C-C and
H-N are not)

No interaction is observed if coupling parts are separated

by more than two bonds

Coupling requires that the vibration be of the same

symmetry
8

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
2. Mechanical Coupling
For example, the calculated and observed for most C=C
bonds is around 1650 cm-1
Butadiene (where the two C=C systems are separated by a
dissimilar C-C bond) the bands are observed at 1640 cm-1
(slight reduction due to resonance, which we will discuss
later)

In allene however, mechanical coupling of the two C=C

systems gives two IR bands at 1960 and 1070 cm-1 due to
H
mechanical coupling
H
C
H

C
H

For purposes of this course, when we discuss the group

9
frequencies, we will point out when this occurs

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
3. Fermi Resonance
A Fermi Resonance is a special case of mechanical coupling

It is often called an accidental degeneracy

In understanding this, for many IR bands, there are

overtones of the fundamental (the vs you are taught) at
twice the wavenumber

In a good IR spectrum of a ketone (2-hexanone, here) you

will see a C=O stretch at 1715 cm-1 and a small peak at
3430 cm-1 for the overtone
overtone

fundamental

10

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
3. Fermi Resonance
Ordinarily, most overtones are so weak as not to be
observed

But, if the overtone of a particular vibration coincides with

the band from another vibration, they can couple and
cause a shift in group frequency and introduce extra bands

If you first looked at the IR (working cold) of benzoyl

chloride, you may deduce that there were two dissimilar
C=O bonds in the molecule

O
C
Cl

11

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
3. Fermi Resonance
In this spectrum, the out of plane bend of the aromatic C-H
bonds occurs at 865 cm-1; the overtone of this band
coincides with the fundamental of C=O at 1730 cm-1

The band is split by Fermi resonance (1760 and 1720 cm1

)

O
C
Cl

12

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
3. Fermi Resonance
Again, we will cover instances of this in the discussion of
group frequencies, but this occurs often in IR of organics
Most observed:
Aldehydes the overtone of the C-H deformation
mode at 1400 cm-1 is always in Fermi resonance with
the stretch of the same band at 2800 cm-1

O
C
H

13
The N-H stretching mode of (C=O)-NH- in polyamides

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
4. Hydrogen Bonding
One of the most common effects in chemistry, and can
change the shape and position of IR bands

Internal (intramolecular) H-bonding with carbonyl

compounds can serve to lower the absorption frequency
CH3
O

1680 cm-1
O
H

CH3
O

1724 cm-1
O

14

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
4. Hydrogen Bonding
Inter-molecular H-bonding serves to broaden IR bands due
to the continuum of bond strengths that result from
autoprotolysis

Compare the two IR spectra of 1-propanol; the first is an IR

of a neat liquid sample, the second is in the gas phase
note the shift and broadening of the O-H stretching band

Gas phase

Neat liquid

15

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
4. Hydrogen Bonding
Some compound, in addition to intermolecular effects for
the monomeric species can form dimers and oligomers
which are also observded in neat liquid samples

Carboxylic acids are the best illustrative example the

broadened O-H stretching band will be observed for the
monomer, dimer and oligomer
H
O

Monomer

H
O

O
H

Dimer

O
H

Oligomer

O
H

16

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
5. Ring Strain
Certain functional group frequencies can be shifted if one
of the atoms hybridization is affected by the constraints of
bond angle in ring systems

Consider the C=O band for the following cycloalkanones:

1815
cm-1

1775

1750

1715

1705

We will discuss the specific cases for these shifts during

our coverage of group frequencies

17

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
6. Electronic Effects - Inductive
The presence of a halogen on the -carbon of a ketone (or
electron w/d groups) raises the observed frequency for the
-bond

Due to electron w/d the carbon becomes more electron

deficient and the -bond compensates by tightening
O
C

18

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
6. Electronic Effects - Resonance
One of the most often observed effects

Contribution of one of the less good resonance forms of

an unsaturated system causes some loss of p-bond
strenght which is seen as a drop in observed frequency
O
C
C C

vs.

O
C
C C

O
O

1684 cm-1
C=O

1715 cm-1
C=O

19

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
6. Electronic Effects - Resonance
In extended conjugated systems, some resonance
contributors are out-of-sync and do not resonate with a
group

Example:
O
C

X=

H3C

H2N

O
C CH3

Strong resonance contributor

NH2

CH3

Cl

NO2

1677

1687

1692

1700

O
N

vs.
O

cm-1

O
C
CH3

Poor resonance contributor

(cannot resonate with C=O)

20

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
6. Electronic Effects - Sterics
Consider this example:
O

CH3
C=O: 1686 cm-1

C=O: 1693 cm-1

In this case the presence of the methyl group mis-aligns

the conjugated system, and resonance cannot occur as
efficiently

The effects of induction, resonance and sterics are very

case-specific and can yield a great deal of information
about the electronic structure of a molecule

21

IR Spectroscopy
Monday we will finish a few more effects and do instrument design
It looks like we wont get to group frequencies until late Monday or Wednesday
The next exam would be delayed to compensate
It is your choice for this occurrence whether the exam would be the day after the last
workshop on the material or a following Monday
Mass Spectrometry and UV would be shortened to compensate
Aside: Make sure you are using the right print parameters to save ink and preserve
clarity of the lecture handouts!!!

22

IR Spectroscopy

23