Introduction to Infrared Spectroscopy

• When light interacts with molecules, the effect depends on

the wavelength of light used

(Nuclear/Electronic spin)

(Vibrational)

(Electronic)

• This portion focuses on IR spectroscopy

Electromagnetic Spectrum

Vibrational IR 2500 25000 nm

400 4000 cm-1 (Wavenumbers)
Infrared Radiations

• Some night vision goggles can detect IR light that is emitted

• IR or thermal imaging is also used to detect breast cancer
Infrared Spectroscopy

Introduction: The IR Spectroscopic Process

 The quantum mechanical energy levels observed in IR spectroscopy

are those of molecular vibration (8 to 40 kJ/mole)
 When we say a covalent bond between two atoms is of a certain
length, we are citing an average because the bond behaves as if it
were a vibrating spring connecting the two atoms
 For a simple diatomic molecule, this model is easy to visualize:
Infrared Spectroscopy
The IR Spectroscopic Process:
 There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric
(2853 cm-1) (2926 cm-1)

• Bend – Vibration or oscillation not along the line of the bond

H H H H
C C C C
H H H
H
(1450 cm-1) scissor rock (720 cm-1) (1250 cm-1) twist wag (1250 cm-1)
in plane out of plane
Illustration of Molecular Vibrations

(2872 cm-1) (2962 cm-1)

http://www.chem.purdue.edu/gchelp/vibs/co2.html
Infrared Spectroscopy

The IR Absorption Process:

 As a covalent bond oscillates – due to the oscillation of the dipole of the

molecule – a varying electromagnetic field is produced

 The greater the dipole moment change through the vibration, the more
intense the EM field that is generated
Infrared Spectroscopy
The IR Spectroscopic Process:

 When a wave of infrared light encounters this oscillating EM field

generated by the oscillating dipole of the same frequency, the
two waves couple, and IR light is absorbed

 The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

“coupled” wave Will not absorb IR

EM oscillating wave
from bond vibration
Infrared Spectroscopy

Typical IR spectrum for Organic Molecule

- many more bands than in UV-vis, fluorescence or phosphorescence
- bands are also much sharper
- pattern is distinct for given molecule
• except for optical isomers
- good qualitative tool
• can be used for compound identification
• group analysis – structural information
- also quantitative tool
• intensity of bands related to amount of compound present
- spectra usually shown as percent transmittance (instead of absorbance)
vs. wavenumber (instead of λ) for convenience
Infrared Spectroscopy
The IR Spectrum:

 Each stretching and bending vibration occurs with a characteristic frequency

as the atoms and charges involved are different for different bonds in compounds

The y-axis on an IR
spectrum is in units of
% transmittance In regions where
no osc. bond is
interacting with
In regions where the EM IR light,
field of an osc. bond transmittance
interacts with IR light nears 100%
of the same ν –
transmittance is low
(light is absorbed)
Infrared Spectroscopy

The IR Spectrum:

 The x-axis of the IR spectrum is in units of wavenumbers, ν, which is the number

of waves per centimeter in units of cm-1 (Remember, E = hν or E = hc/λ)

Wavenumber, Intensity, and Shape

Infrared Spectroscopy

The IR Spectrum:

 This unit is used rather than wavelength (microns) because wavenumbers are
directly proportional to the energy of transition being observed – chemists like
this, physicists hate it!

High frequencies and high wavenumbers equate higher energy

is quicker to understand than

Short wavelengths equate higher energy

 This unit is used rather than frequency as the numbers are more “real” than the
exponential units of frequency

 IR spectra are observed for the mid-infrared: 600-4000 cm-1

 The peaks are Gaussian distributions of the average energy of a transition

Infrared Spectroscopy

The IR Spectrum – The detection of different bonds

 As opposed to chromatography or other spectroscopic methods, the

area of a IR band (or peak) is not directly proportional to concentration
of the functional group producing the peak

 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

• Typically, stretching will change dipole moment more than

bending

• The greater the difference in electronegativity between the

atoms involved in bonding, the larger the dipole moment

• For both effects, the greater the change in dipole moment in

a given vibration or bend, the larger the peak
Infrared Spectroscopy

The IR Spectrum – The detection of different bonds

It is important to make note of peak intensities to show the effect of these factors:

• Strong (s) – peak is tall, transmittance is low (0-35 %)

• Medium (m) – peak is mid-height (75-35%)

• Weak (w) – peak is short, transmittance is high (90-75%)

• * Broad (br) – if the Gaussian distribution is abnormally broad

(*this is more for describing a bond that spans many energies)

Exact transmittance values are rarely recorded

Infrared Spectroscopy
The IR Spectrum:

 In general: Lighter atoms will allow the oscillation to be faster – higher

energy. This is especially true of bonds to hydrogen – C-H, N-H and O-H

 Stronger bonds will have higher energy oscillations

Triple bonds > double bonds > single bonds in energy

Energy/ν of oscillation
• One can rationalize the trends below using the wavenumber formula
(Hooke’s Law)

1. (Mass)

2. (Bond strength)

(Hybridization/Resonance effects)
Bond stretching frequencies
• The energy necessary to cause absorption (vibration) depends on the
type of bond
Infrared Spectroscopy

Infrared Group Analysis

General

1. The primary use of the IR is to detect functional groups

2. Because the IR looks at the interaction of the EM spectrum with actual

bonds, it provides a unique qualitative probe into the functionality of a
molecule, as functional groups are merely different configurations of
different types of bonds

3. Since most “types” of bonds in covalent molecules have roughly the same
energy, i.e., C=C and C=O bonds (1715 ± 100 cm-1), C-H and N-H bonds
(3000 ± 150 cm-1) they show up in similar regions of the IR spectrum

4. Remember all organic functional groups are made of multiple bonds and
therefore show up as multiple IR bands (peaks)
Infrared Group Analysis

 The four primary regions of the IR spectrum

Bonds to H Triple bonds Double bonds Single Bonds

Fingerprint
Region

O-H C≡C C=O C-C

N-H C≡N C=N C-N
C-H X=C=Y C=C C-O
(C, O, N, S) C-Cl

4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 600 cm-1
 Fingerprint Region

Fingerprint Region (~1500-500 cm-1)

 region of most single bond signals
 many have similar frequencies, so
affect each other & give pattern
characteristics of overall skeletal
structure of a compound
 exact interpretation of this region of
spectra seldom possible because of
complexity
 complexity  uniqueness
Group frequency Region (~1500-4000 cm-1)
Abbreviated Table of Group Frequencies for Organic Groups

Bond Type of Compound Frequency Range, cm-1 Intensity

C-H Alkanes 2850-2970 Strong
C-H Alkenes H 3010-3095 Medium
C C
675-995 strong
Base values for absorptions of bonds
C-H Alkynes C C H 3300 Strong

C-H Aromatic rings 3010-3100 Medium

690-900 strong
0-H Monomeric alcohols, phenols 3590-3650 Variable
Hydrogen-bonded alchohols, phenols 3200-3600 Variable, sometimes broad
Monomeric carboxylic acids 3500-3650 Medium
Hydrogen-bonded carboxylic acids 2500-2700 broad
N-H Amines, amides 3300-3500 medium
C=C Alkenes 1610-1680 Variable
C=C Aromatic rings 1500-1600 Variable
C C Alkynes 2100-2260 Variable
C-N Amines, amides 1180-1360 Strong
C N Nitriles 2210-2280 Strong
C-O Alcohols, ethers,carboxylic acids, esters 1050-1300 Strong
C=O Aldehydes, ketones, carboxylic acids, esters 1690-1760 Strong
NO2 Nitro compounds 1500-1570 Strong
1300-1370
Infrared Spectrophotometer and Sampling
Ratio of Is and Ir

Continuous
Hot wire spectrum of ν

Varies ν

FT-IR/ATR

Liquids/Solids – Salt (KBr/NaCl) plates/KBr Pellet/Nujol Mull (mineral oil)