Infrared: Interpretation

Infrared spectroscopy is the study of the interaction of infrared light with matter. The fundamental measurement
obtained in infrared spectroscopy is an infrared spectrum, which is a plot of measured infrared intensity versus
wavelength (or frequency) of light.

Introduction
In infrared spectroscopy, units called wavenumbers are normally used to denote different types of light. The
frequency, wavelength, and wavenumber are related to each other via the following equation(1):

(1)
These equations show that light waves may be described by their frequency, wavelength or wavenumber. Here,
we typically refer to light waves by their wavenumber, however it will be more convenient to refer to a light wave's
frequency or wavelength. The wavenumber of several different types of light are shown in table 1.

Table 1. The Electromagnetic spectrum showing the wavenumber of several different types of light.

When a molecule absorbs infrared radiation, its chemical bonds vibrate. The bonds can stretch, contract, and
bend. This is why infrared spectroscopy is a type of vibrational spectroscopy. Fortunately, the complex vibrational
motion of a molecule can be broken down into a number of constituent vibrations called normal modes. For
example, when a guitar string is plucked, the string vibrates at its normal mode frequency. Molecules, like guitar
strings, vibrate at specfic frequencies so different molecules vibrate at different frequencies because their
structures are different. This is why molecules can be distinguished using infrared spectroscopy. The first
necessary condition for a molecule to absorb infrared light is that the molecule must have a vibration during
which the change in dipole moment with respect to distance is non-zero. This condition can be summarized in
equation(2) form as follows:

(2)
Vibrations that satisfy this equation are said to be infrared active. The H-Cl stretch of hydrogen chloride and the
asymmetric stretch of CO2are examples of infrared active vibrations. Infrared active vibrations cause the bands
seen in an infrared spectrum.
The second necessary condition for infrared absorbance is that the energy of the light impinging on a molecule
must equal a vibrational energy level difference within the molecule. This condition can be summarized in
equation(3) form as follows:

(3)
If the energy of a photon does not meet the criterion in this equation, it will be transmitted by the sample and if
the photon energy satisfies this equation, that photon will be absorbed by the molecule.(See Infrared: Theory for
more detail)
As any other analytical techniques, infrared spectroscopy works well on some samples, and poorly on others. It is
important to know the strengths and weaknesses of infrared spectroscopy so it can be used in the proper way.
Some advantages and disadvantages of infrared spectroscopy are listed in table 2.
Advantages

Disadvantages

Solids, Liquids, gases, semi-solids, powders and polymers are all

analyzed

Atoms or monatomic ions do not have infrared spectra

Homonuclear diatomic molecules do not posses infrared spectra

The peak positions, intensities, widths, and shapes all provide

useful information

Complex mixture and aqueous solutions are difficult to analyze using

infrared spectroscopy

Fast and easy technique

Sensitive technique (Micrograms of materials can be detected
routinely)
Inexpensive
Table 2. The Advantage and Disadvantage of Infrared Spectroscopy

The Orgin of Infrared Peak Positions,

Intensities, and Widths
Peak Positions
The equation(4) gives the frequency of light that a molecule will absorb, and gives the frequency of vibration of
the normal mode excited by that light.

(4)
Only two variables in equation(4) are a chemical bond's force constant and reduced mass. Here, the reduced
mass refers to (M1M2)/(M1+M2) where M1 and M2 are the masses of the two atoms, respectively. These two
molecular properties determine the wavenumber at which a molecule will absorb infrared light. No two chemical
substances in the universe have the same force constants and atomic masses, which is why the infrared
spectrum of each chemical substance is unique. To understand the effect of atomic masses and force constant
on the positions of infrared bands, table 3 and 4 are shown as an example, respectively.
Table 3. An Example of an Mass Effect
Bond

C-H Stretch in cm-1

C-1H

~3000

C-2D

~2120

The reduced masses of C-1H and C-2D are different, but their force constants are the same. By simply doubling
the mass of the hydrogen atom, the carbon-hydrogen stretching vibration is reduced by over 800cm-1.

Table 4. An Example of an electronic Effect

Bond

C-H Stretch in cm-1

C-H

~3000

H-C=O

~2750

When a hydrogen is attached to a carbon with a C=O bond, the C-H stretch band position decrease to ~2750cm 1
. These two C-H bonds have the same reduced mass but different force constants. The oxygen in the second
molecule pulls electron density away from the C-H bond so it makes weaken and reduce the C-H force constant.
This cause the C-H stretching vibration to be reduced by ~250cm-1.

The Origin of Peak Intensities

The different vibrations of the different functional groups in the molecule give rise to bands of differing intensity.
This is because x is different for each of these vibrations. For example, the most intense band in the spectrum
of octane shown in Figure 3 is at 2971, 2863 cm-1 and is due to stretching of the C-H bond. One of the weaker
bands in the spectrum of octane is at 726cm -1, and it is due to long-chain methyl rock of the carbon-carbon bonds
in octane. The change in dipole moment with respect to distance for the C-H stretching is greater than that for the
C-C rock vibration, which is why the C-H stretching band is the more intense than C-C rock vibration.
Another factor that determines the peak intensity in infrared spectra is the concentration of molecules in the
sample. The equation(5) that relates concentration to absorbance is Beer's law,

(5)
The absorptivity is the proportionality constant between concentration and absorbance, and is dependent on
2
(/x) . The absorptivity is an absolute measure of infrared absorbance intensity for a specific molecule at a
specific wavenumber. For pure sample, concentation is at its maximum, and the peak intensities are true

representations of the values of /x for different vibrations. However, in a mixture, two peaks may have
different intensities because there are molecules present in different concentration.

The Orgins of Peak Widths

In general, the width of infrared bands for solid and liquid samples is determined by the number of chemical
environments which is related to the strength of intermolecular interactions such as hydrogen bonding. Figure
1. shows hydrogen bond in water molecules and these water molecules are in different chemical environments.
Because the number and strength of hydrogen bonds differs with chemical environment, the force constant varies
and the wavenumber differs at which these molecules absorb infrared light.

Figure 1. Hydrogen Bonding in water molecules

In any sample where hydrogen bonding occurs, the number and strength of intermolecular interactions varies
greatly within the sample, causing the bands in these samples to be particularly broad. This is illustrated in the
spectra of ethanol(Fig7) and hexanoic acid(Fig11). When intermolecular interactions are weak, the number of
chemical environments is small, and narrow infrared bands are observed.

The Origin of Group Frequencies

An important observation made by early researchers is that many functional group absorb infrared radiation at
about the same wavenumber, regardless of the structure of the rest of the molecule. For example, C-H stretching
vibrations usually appear between 3200 and 2800cm -1 and carbonyl(C=O) stretching vibrations usually appear
between 1800 and 1600cm-1. This makes these bands diagnostic markers for the presence of a functional group
in a sample. These types of infrared bands are called group frequencies because they tell us about the presence
or absence of specific functional groups in a sample.

Figure 2. Group frequency and fingerprint regions of the mid-infrared spectrum

The region of the infrared spectrum from 1200 to 700 cm -1 is called the fingerprint region. This region is notable
for the large number of infrared bands that are found there. Many different vibrations, including C-O, C-C and CN single bond stretches, C-H bending vibrations, and some bands due to benzene rings are found in this region.
The fingerprint region is often the most complex and confusing region to interpret, and is usually the last section
of a spectrum to be interpreted. However, the utility of the fingerprint region is that the many bands there provide
a fingerprint for a molecule.

Spectral Interpretation by Application of

Group Frequencies
Organic Compounds
One of the most common application of infrared spectroscopy is to the identification of organic compounds. The
major classes of organic molecules are shown in this category and also linked on the bottom page for the number
of collections of spectral information regarding organic molecules.
Hydrocarbons
Hydrocarbons compounds contain only C-H and C-C bonds, but there is plenty of information to be obtained from
the infrared spectra arising from C-H stretching and C-H bending.
In alkanes, which have very few bands, each band in the spectrum can be assigned:

CH stretch from 30002850 cm-1

CH bend or scissoring from 1470-1450 cm-1
CH rock, methyl from 1370-1350 cm-1
CH rock, methyl, seen only in long chain alkanes, from 725-720 cm-1
Figure 3. shows the IR spectrum of octane. Since most organic compounds have these features, these C-H
vibrations are usually not noted when interpreting a routine IR spectrum. Note that the change in dipole moment
with respect to distance for the C-H stretching is greater than that for others shown, which is why the C-H stretch
band is the more intense.

Figure 3. Infrared Spectrum of Octane

In alkenes compounds, each band in the spectrum can be assigned:

C=C stretch from 1680-1640 cm-1

=CH stretch from 3100-3000 cm-1
=CH bend from 1000-650 cm-1
Figure 4. shows the IR spectrum of 1-octene. As alkanes compounds, these bands are not specific and are
generally not noted because they are present in almost all organic molecules.

Figure 4. Infrared Spectrum of 1-Octene

In alkynes, each band in the spectrum can be assigned:

C?C stretch from 2260-2100 cm-1

C?CH: CH stretch from 3330-3270 cm-1
C?CH: CH bend from 700-610 cm-1
The spectrum of 1-hexyne, a terminal alkyne, is shown below.

Figure 5. Infrared Spectrum of 1-Hexyne

In aromatic compounds, each band in the spectrum can be assigned:

CH stretch from 3100-3000 cm-1

overtones, weak, from 2000-1665 cm-1
CC stretch (in-ring) from 1600-1585 cm-1
CC stretch (in-ring) from 1500-1400 cm-1
CH "oop" from 900-675 cm-1
Note that this is at slightly higher frequency than is the CH stretch in alkanes. This is a very useful tool for
interpreting IR spectra. Only alkenes and aromatics show a CH stretch slightly higher than 3000 cm-1.
Figure 6. shows the spectrum of toluene.

Figure 6. Infrared Spectrum of Toluene

Functional Groups Containing the C-O Bond

Alcohols have IR absorptions associated with both the O-H and the C-O stretching vibrations.

OH stretch, hydrogen bonded 3500-3200 cm-1

CO stretch 1260-1050 cm-1 (s)
Figure 7. shows the spectrum of ethanol. Note the very broad, strong band of the OH stretch.

Figure 7. Infrared Spectrum of Ethanol

The carbonyl stretching vibration band C=O of saturated aliphatic ketones appears:

C=O stretch - aliphatic ketones 1715 cm-1

- ?, ?-unsaturated ketones 1685-1666 cm-1

Figure 8. shows the spectrum of 2-butanone. This is a saturated ketone, and the C=O band appears at 1715.

Figure 8. Infrared Spectrum of 2-Butanone

If a compound is suspected to be an aldehyde, a peak always appears around 2720 cm -1 which often appears as
a shoulder-type peak just to the right of the alkyl CH stretches.

o
o

HC=O stretch 2830-2695 cm-1

C=O stretch:
aliphatic aldehydes 1740-1720 cm-1
alpha, beta-unsaturated aldehydes 1710-1685 cm-1
Figure 9. shows the spectrum of butyraldehyde.

Figure 9. Infrared Spectrum of Butyraldehyde

The carbonyl stretch C=O of esters appears:

o
o

C=O stretch
aliphatic from 1750-1735 cm-1
?, ?-unsaturated from 1730-1715 cm-1
CO stretch from 1300-1000 cm-1
Figure 10. shows the spectrum of ethyl benzoate.

Figure 10. Infrared Spectrum of Ethyl benzoate

The carbonyl stretch C=O of a carboxylic acid appears as an intense band from 1760-1690 cm-1. The exact
position of this broad band depends on whether the carboxylic acid is saturated or unsaturated, dimerized, or has
internal hydrogen bonding.

OH stretch from 3300-2500 cm-1

C=O stretch from 1760-1690 cm-1
CO stretch from 1320-1210 cm-1
OH bend from 1440-1395 and 950-910 cm-1
Figure 11. shows the spectrum of hexanoic acid.

Figure 11. Infrared Spectrum of Hexanoic acid

Organic Nitrogen Compounds

NO asymmetric stretch from 1550-1475 cm-1

NO symmetric stretch from 1360-1290 cm-1

Figure 12. Infrared Spectrum of Nitomethane

Organic Compounds Containing Halogens

Alkyl halides are compounds that have a CX bond, where X is a halogen: bromine, chlorine, fluorene, or iodine.

o
o

CH wag (-CH2X) from 1300-1150 cm-1

CX stretches (general) from 850-515 cm-1
CCl stretch 850-550 cm-1
CBr stretch 690-515 cm-1
The spectrum of 1-chloro-2-methylpropane are shown below.

Figure 13. Infrared Spectrum of 1-chloro-2-methylpropane

For more Infrared spectra Spectral database of organic molecules is introduced to use free database. Also,
the infrared spectroscopy correlation tableis linked on bottom of page to find other assigned IR peaks.

Inorganic Compounds
Generally, the infrared bands for inorganic materials are broader, fewer in number and appear at lower
wavenumbers than those observed for organic materials. If an inorganic compound forms covalent bonds within
an ion, it can produce a characteristic infrared spectrum.
Main infrared bands of some common inorganic ions:

CO32SO42-

1450-1410, 880-800cm-1
1130-1080, 680-610cm-1

NO3PO43-

1410-1340, 860-800cm-1
1100-950cm-1

SiO4 NH4+

1100-900cm-1
3335-3030, 1485-1390cm-1

MnO4-

920-890, 850-840cm-1

Diatomic molecules produce one vibration along the chemical bond. Monatomic ligand, where metal s coordinate
with atoms such as halogens, H, N or O, produce characteristic bands. These bands are summarized in below.

Chracteristic infrared bands of diatomic inorganic molecules: M(metal), X(halogen)

M-H stretching

2250-1700cm-1

M-H bending
M-X stretching

800-600cm-1
750-100cm-1

M=O stretching
M=N stretching

1010-850cm-1
1020-875cm-1

The normal modes of vibration of linear and bent triatomic molecules are illustrated and some common linear and
bent triatomic molecules are shown below. Note that some molecules show two bands for ?1because of Fermi
resonance.
Characteristic infrared bands(cm-1) of triatomic inorganic molecules:
Linear Molecules

OCO

NCS-

HCN

ClCN

MgCl2
1388,
1286

3311
053

784

667

712

486, 471

380

2
714,

327

249

2349

2049

748

2219

842

Bent
Molecules
O3

H2O
SnCl 2
3675

1135

354

1595
716

120

3756

1089

334

Identification
There are a few general rules that can be used when using a mid-infrared spectrum for the determination of a
molecular structure. The following is a suggested strategy for spectrum interpretation: 2
1.

Look first at the high-wavenumber end of the spectrum(>1500cm-1) and concentrate initially on the major bands

2.
3.

For each band, 'short-list' the possibilities by using a correlation table

Use the lower-wavenumber end of the spectrum for the confirmation or elaboration of possible structural

4.

elements
Do not expect to be able to assign every band in the spectrum

5.
6.

Keep 'cross-checking' wherever possible.

Exploit negative evidence as well as positive evidence

7.

Band intensities should be treated with some caution. Under certain circumstances, they may vary considerably
for the same group

8.
9.

Take care when using small wavenumber changes. If in solution, some bands are very 'solvent-sensitive'
Do not forget to subtract slovent bands if possible
Infrared spectroscopy is used to analyze a wide variety of samples, but it cannot solve every chemical analysis
problem. When used in conjunction with other methods such as mass spectroscopy, nuclear magnetic
resonance, and elemental analysis, infrared spectroscopy usually makes possible the positive identification of a
sample.

References
1.
2.

Infrared Spectral Interpretation by Brian Smith, CRC Press, 1999

Infrared Spectroscopy: Fundamentals and Applications by Barbara Atuart, John Wiley&Sons, Ltd., 2004

3.

Interpretation of Infrared Spectra, A Practical Approach by John Coates in Encyclopedia of Analytical Chemistry
pp. 10815-10837, John Wiley&Sons Ltd, Chichester, 2000

Outside Links

Spectral Database for Organic Compounds SDBS: http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of

Advanced Industrial Science and Technology, date of access)

o
o

Infrared Spectroscopy Correlation Table: http://en.wikipedia.org/wiki/Infrared_spectroscopy_correlation_table

FDM Reference Spectra Databases: http://www.fdmspectra.com/index.html
Other Usuful Web Pages:
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/InfraRed/infrared.htm
Fermi resonance : http://en.wikipedia.org/wiki/Fermi_resonance

http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscopy/Infrared_
Spectroscopy/Infrared%3A_Theory

Infrared: Theory
Infrared (IR) spectroscopy is one of the most common and widely used spectroscopic techniques employed
mainly by inorganic and organic chemists due to its usefulness in determining structures of compounds and
identifying them. Chemical compounds have different chemical properties due to the presence of different
functional groups.
1.
1.

1. Introduction
1.1. Absorption Spectroscopy

2.
1.

1.2. Molecular Vibrations

1.2.1. Diatomic Molecular Vibration

2.
3.

1.2.2. Polyatomic Molecular Vibration

1.2.3. Quantum Mechanics

1.
2.

1.2.3.1. The Deduction of Frequency

1.2.3.2. The Deduction of Wave Number

2.
3.

2. History of IR
3. Theory of IR

4.
5.

4. Region of IR
5. IR Analysis

1.
2.

5.1. Qualitative Analysis

5.2. Quantitative Analysis

6.
7.

6. IR Instrumentation
7. Selection Rules of IR

8.
9.

8. Influence Factors of IR
9. Advantages of IR

10. 10. Disadvantages of IR

11. 11. Symmetry & IR Spectroscopy
1.
2.

11.1. Question
11.2. Answer

12. 12. Problems

13. 13. References
14. 14. Outside Links
15. 15. Contributors

Introduction
Infrared (IR) spectroscopy is one of the most common and widely used spectroscopic techniques. Absorbing
groups in the infrared region absorb within a certain wavelength region. The absorption peaks within this region
are usually sharper when compared with absorption peaks from the ultraviolet and visible regions. In this way, IR
spectroscopy can be very sensitive to determination of functional groups within a sample since different
functional group absorbs different particular frequency of IR radiation. Also, each molecule has a characteristic
spectrum often referred to as the fingerprint. A molecule can be identified by comparing its absorption peak to a
data bank of spectra. IR spectroscopy is very useful in the identification and structure analysis of a variety of
substances, including both organic and inorganic compounds. It can also be used for both qualitative and
quantitative analysis of complex mixtures of similar compounds.

Absorption Spectroscopy
There are three main processes by which a molecule can absorb radiation. and each of these routes involves an
increase of energy that is proportional to the light absorbed. The first route occurs when absorption of radiation
leads to a higher rotational energy level in a rotational transition. The second route is a vibrational transition
which occurs on absorption of quantized energy. This leads to an increased vibrational energy level. The third
route involves electrons of molecules being raised to a higher electron energy, which is the electronic transition.
Its important to state that the energy is quantized and absorption of radiation causes a molecule to move to a
higher internal energy level. This is achieved by alternating the electric field of the radiation interacting with the
molecule and causing a change in the movement of the molecule. There are multiple possibilities for the different
possible energy levels for the various types of transitions.
The energy levels can be rated in the following order: electronic > vibrational > rotational. Each of these
transitions differs by an order of magnitude. Rotational transitions occur at lower energies (longer wavelengths)
and this energy is insufficient and cannot cause vibrational and electronic transitions but vibrational (near infrared) and electronic transitions (ultraviolet region of the electromagnetic spectrum) require higher energies.
The diagram below illustrates possible transitions that occur.

A Rotational Transitions
B Rotational-Vibrational Transitions
C Rotational-Vibrational-Electronic Transitions
E0 is the electronic ground state and E1 is the electronic excited state.

Figure 1: Energy level Diagram

The energy of IR radiation is weaker than that of visible and ultraviolet radiation, and so the type of radiation
produced is different. Absorption of IR radiation is typical of molecular species that have a small energy
difference between the rotational and vibrational states. A criterion for IR absorption is a net change in dipole
moment in a molecule as it vibrates or rotates. Using the molecule HBr as an example, the charge distribution
between hydrogen and bromine is not evenly distributed since bromine is more electronegative than hydrogen
and has a higher electron density. HBr thus has a large dipole moment and is thus polar. The dipole moment is
determined by the magnitude of the charge difference and the distance between the two centers of charge. As
the molecule vibrates, there is a fluctuation in its dipole moment; this causes a field that interacts with the electric
field associated with radiation. If there is a match in frequency of the radiation and the natural vibration of the
molecule, absorption occurs and this alters the amplitude of the molecular vibration. This also occurs when the
rotation of asymmetric molecules around their centers results in a dipole moment change, which permits
interaction with the radiation field. Molecules such as O 2, N2, Br2, do not have a dipole moment when they
undergo rotational and vibrational motions, as a result, they cannot cannot absorb IR radiation. This is because
they do not have a net gain dipole moment.

Molecular Vibrations
Diatomic Molecular Vibration
The absorption of IR radiation by a molecule can be likened to 2 atoms attached to each other by a massless
spring. Considering simple diatomic molecules, only one vibration is possible. The potential energy VS
antinuclear distance, r can be represented by a Morse curve.

Figure 2: Morse Curve - figure from Wikipedia

The Hook's law potential on the other hand is based on an ideal spring

F=kx
F(x)=dV(x)dx
this results in one dimensional space

V(r)=12k(rreq)
One thing that the Morse and Harmonic have in common is the small displacements (x) from the equilirium.
Solving the Schrdinger equation for the harmonic scillator potential results in the energy levels results in

Ev=(v+12)hve
with v=0,1,2,3.....infinity

ve=12k
When calculating the energy of a diatomic molecule, factors such as anharmonicity (has a similar curve with the
harmonic oscillator at low potential energies but deviates at higher energies) are considered. The energy spacing
in the harmonic oscillator is equal but not so with the anharmonic oscillator. The anharmonic oscillator is a

deviation from the harmonic oscillator. Other considered terms include; centrifugal stretching, vibrational and
rotational interactions have to be taken into account. The energy can be expressed mathematically as

Ev=(v+12)hve(v+12)2Xehve+BeJ(J+1)DeJ2(J+1)2e(v+12)J(J+1)
The first and third terms represent the harmonicity and rigid rotor behavior of a diatomic molecule such as HCl.
The secod term represents anharmonicity and the fourth term represents centrifugal stretching. The fifth term
represents the interaction between the vibration and rotational interaction of the molecule.

Polyatomic Molecular Vibration

The bond of a molecule experiences various types of vibrations and rotations. This causes the atom not to be
stationary and to fluctuate continuously. Vibrational motions are defined by stretching and bending modes. These
movements are easily defined for diatomic or triatomic molecules. This is not the case for large molecules due
to several vibrational motions and interactions that will be experienced. When there is a continuous change in the
interatomic distance along the axis of the bond between two atoms, this process is known as a stretching
vibration. A change in the angle occurring between two bonds is known as a bending vibration. Four bending
vibrations exist namely, wagging, twisting, rocking and scissoring. A CH 2 group is used as an example to illustrate
stretching and bending vibrations below.

Symmetric Stretch

Asymmetric Stretch

Twisting

Wagging

Scissoring

Rocking

Figure 3: Types of Vibrational Modes. Figure from Wikipedia

As stated earlier, molecular vibrations consist of stretching and bending modes. A molecule consisting of (N)
number of atoms has a total of 3N degrees of freedom, corresponding to the cartesian coordinates of each atom
in the molecule. In a non-linear molecule, 3 of these degrees of freedom are rotational, 3 are translational and the
remainder is fundamental vibrations. In a linear molecule, there are 3 translational degrees of freedom and 2 are
rotational. This is because in a linear molecule, all of the atoms lie on a single straight line and hence rotation
about the bond axis is not possible. Mathematically the normal modes for a linear and non linear can be
expressed as

Linear Molecules:

(3N - 5) degrees of freedom

Non-Linear molecules:

(3N - 6) degrees of freedom

Diagram of Stretching and Bending Modes for H2O: H2O molecule is a non-linear molecule due to the uneven
distribution of the electron density. O2 is more electronegative than H2 and carries a negative charge, while H has
a partial positive charge. The total degrees of freedom for H 2O will be 3(3)-6 = 9-6 = 3 degrees of freedom which
correspond to the following stretching and bending vibrations. The vibrational modes are illustrated below:

Figure 4 The vibrational modes of H2O

Diagram of Stretching and Bending Modes for CO2: CO2 is a linear molecule and thus has the formula (3N-5).
It has 4 modes of vibration (3(3)-5). CO2 has 2 stretching modes, symmetric and asymmetric. The CO2 symmetric
stretch is not IR active because there is no change in dipole moment because the net dipole moments are in
opposite directions and as a result, they cancel each other. In the asymmetric stretch, O atom moves away from
the C atom and generates a net change in dipole moments and hence absorbs IR radiation at 2350 cm -1. The
other IR absorption occurs at 666 cm-1. CO2 symmetry with CO2 has a total of four of stretching and bending
modes but only two are seen. Two of its bands are degenerate and one of the vibration modes is symmetric
hence it does not cause a dipole moment change because the polar directions cancel each other. The vibrational
modes are illustrated below:

Figure 5 The vibrational modes of CO2

Quantum Mechanics
The Deduction of Frequency
The second law of Newton states that
where m is the mass and a is the acceleration, acceleration is a 2nd order differential equation of distance with
respect to time. thus "a" can be written as
Substituting this into equation 1 gives
the 2nd order differential equation of this equation is equal to
displacement of mass and time can be stated as
where vm is the natural vibrational frequency and A is the maximum amplitude of the motion. On differenciating a
second time the equation becomes
substituting the two equations above into Newton's second law for a harmonic oscillator,

m(422mAcos 2mt)=k(Acos 2mt)

If we cancel out the two functions y,

4m22m=k

from above, we obtain the natural frequency of the oscillation.

Vm which is the natural frequency of the mechanical oscillator which depends on the force constant of the spring
and the mass of the attached body and independent of energy imparted on the system. when there are two
masses involved in the system then the mass used in the above equation becomes
The vibrational frequency can be rewritten as

The Deduction of Wave Number

Using the harmonic oscillator and wave equations of quantum mechanics, the potential energy can be written as
where h is Planck's constant and v is the vibrational quantum number. V = 0,1,2,3.
where vm is the vibrational frequency. Transitions in vibrational energy levels can be brought about by absorption
of radiation, provided the energy of the radiation exactly matches the difference in energy levles between the
vibrational quantum states and provided the vibration causes a change in dipole moment. This can be expressed
as
At room temperature, the majority of molecules are in the ground state v = 0, from the equation above
following the selection rule, when a molecule absorbs energy, there is a promotion to the first excited state
The frequency of radiation v that will bring about this change is identical to the classical vibrational frequency of
the bond vm and it can be expressed as
The above equation can be modified so that the radiation can be expressed in wave numbers
where c is the velocity of light (cm s-1) and
is the wave number of an absoprtion maximum (cm-1)

History of IR
Below is a timeline illustrating the significant events in the history of Infrared spectroscopy. The discovery and
development of Infrared spectroscopy is of great importance to the spectroscopic analysis.

Figure 6 History of Infrared Spectroscopy

Theory of IR
Molecular vibrational frequencies lie in the IR region of the electromagnetic spectrum, and they can be measured
using the IR technique. In IR, polychromatic light (light having different frequencies) is passed through a sample
and the intensity of the transmitted light is measured at each frequency. When molecules absorb IR radiation,
transitions occur from a ground vibrational state to an excited vibrational state. (see figure 1)
In order for a molecule to be IR active there must be a change in dipole moment as a result of the vibration that
occurs when IR radiation is absorbed. Dipole moment is a vector quantity and depends on the orientation of the
molecule and the photon electric vector. The dipole moment changes as the bond expands and contracts. When
all molecules are aligned as in a crystal and the photon vector points along a molecular axis such as z.
Absorption occurs for the vibrations that displace the dipole along z. Vibrations that are totally x or y polarized
would be absent. Dipole moment in a heteronuclear diatomic molecule can be described as uneven distribution of
electron density between the atoms. One atom is more electronegative than the other and has a net negative
charge.
The dipole moment can be expressed mathematically as
The relationship between IR intensity and dipole moment is given as
relating this to intensity of the IR radiation, we have have the following equation below.

where
is the dipole moment and Q is the vibrational coordinate. The transition moment integral for IR can also be
written as
the transition moment integral gives information about the probability of a transition occuring. i and f represent are
initial and final states.
is the wave function. Relating this to IR intensity we have
where
is the dipole moment and has the cartesian coordinates, ,, . In order for a transition to occur by dipole selection
rules , at least one of the integrals must be non zero.

Region of IR
The IR region of the electromagnetic spectrum ranges in wavelength from 2 -15 m. Conventionally the IR region
is subdivided into three regions, near IR, mid IR and far IR. Most of the IR used originates from the mid IR
region. The table below indicates the IR spectral regions
Region

Wavelength Wavenumbers (V), cm-1 Frequencies (v), HZ

Near

0.78 -2.5

12800 - 4000

3.8 x 1014 - 1.2 x 1014

Middle

2.5 - 50

4000 - 200

3.8 x 1014 - 1.2 x 1014

Far

50 -100

200 -10

3.8 x 1014 - 1.2 x 1014

4000 -670

3.8 x 1014 - 1.2 x 1014

Most Used 2.5 -15

IR deals with the interaction between a molecule and radiation from the electromagnetic region ranging (4000- 40
cm-1). The cm-1 is the wave number scale and it can also be defined as 1/wavelength in cm. A linear wavenumber
is often used due to its direct relationship with both frequency and energy. The frequency of the absorbed
radiation causes the molecular vibrational frequency for the absorption process. The relationship is given below

Near InfraRed Spectroscopy

Absorption bands in the near infrared (NIR) region (750 - 2500 nm) are weak

because they arise from vibrational overtones and combination bands. Combination bands occur when two
molecular vibrations are excited simultaneously. The intensity of overtone bands reduces by one order of
overtone for each successive overtone. When a molecule is excited from the ground vibrational state to a higher
vibrational state and the vibrational quantum number v is greater than or equal to 2 then an overtone absorption
results. The first overtone results from v = 0 to v = 2. The second overtone occurs when v =0 transitions to v = 3.
Transitions arising from the near ir absorption are weak, hence they are referred to as forbidden transitions but
these transitions are relevant when non-destructive measurements are required such as a solid sample. Near IR
spectra though have low absorption they have a high signal to noise ratio owing to intense radiation sources and

NIR is able to penetrate undiluted samples and use longer path lengths; it becomes very useful for rapid
measurement of more representative samples.
Far InfraRed Spectroscopy The far IR region is particularly useful for inorganic studies due to stretching and
bending vibrations of bonds between the metal atoms and ligands. The frequencies, which these vibrations are

observed, are usually lower than 650 cm-1. Pure rotational absorption of gases is observed in the far IR region
when there is a permanent dipole moment present. Examples include H 2O, O3, HCl.

IR Analysis
Qualitative Analysis
IR spectroscopy is a great method for identification of compounds, especially for identification of functional
groups. Therefore, we can use group frequencies for structural analysis. Group frequencies are vibrations that
are associated with certain functional groups. It is possible to identify a functional group of a molecule by
comparing its vibrational frequency on an IR spectrum to an IR stored data bank.
Here, we take the IR spectrum of Formaldehyde for an example. Formaldehyde has a C=O functional group and
C-H bond. The value obtained from the following graph can be compared to those in reference data banks stored
for Formaldehyde. A molecule with a C=O stretch has an IR band which is usually found near 1700cm-1 and
around 1400cm-1 for CH2 bend. It's important to note that this value is dependent on other functional groups
present on the molecule. The higher 1700cm-1 indicates a large dipole moment change. It is easier to bend a
molecule than stretch it, hence stretching vibrations have higher frequencies and require higher energies than
bending modes. The finger print region is a region from 1400-650 cm-1. Each molecule has it's own characteristic
print and is often cumbersome to attach any values to this region.

Figure 6 IR Spectrum of Formaldehyde

Quantitative Analysis
Infrared spectroscopy can also be applied in the field of quantitative analysis, although sometimes it's not as
accurate as other analytical methods, like gas chromatography and liquid chromatography. The main theory of IR
quantification is Beer's law or Beer-Lambert law, which is written as

A=log(I0I)=lc
Where A is the absorbance of the sample, I is the intensity of transmitted light, I 0 is the intensity of incident light, l
is the path length, a is the molar absorptivity of the substance, and c is the concentration of the substance.
From the Beer's Law, we could figure out the relation between the absorbance and the concentration of the
sample since the analytes have a particular molar absorptivity at a particular wavelength. Therefore, we could
use IR spectroscopy and Beer's Law to find the concentration of substance or the components of mixture. This is
how the IR quantification operated.

IR Instrumentation
Infrared Spectrometers take advantage of the characteristic IR absorption of chemical compounds to analyze the
structural information and composition of substances. Like other radiation spectrometers, its usually composed
of four parts: light source, to produce a beam of infrared light; monochromator, to isolate a single wavelength of
radiation; detector, to detect the signals; PC, computer connected with the spectrometer to process the spectra
information.

Figure 7 Experimental Details of IR Spectroscopy

Selection Rules of IR
In order for vibrational transitions to occur, they are normally governed by some rules referred to as selection
rules.
1.

1. An interaction must occur between the oscillating field of the electromagnetic radiation and the vibrational
molecule for a transition to occur. This can be expressed mathematically as
and

2.

This holds for a harmonic oscillator because the vibrational levels are equally spaced and that accounts for the
single peak observed in any given molecular vibration. For gases J changes +1 for the R branch and -1 for the
P branch. is a fordidden transistion and hence a q branch for a diatomic will not be present. For any anharmonic
oscillator, the selection rule is not followed and it follows that the change in energy becomes smaller. This results
in weaker transitions called overtones, then (first overtone) can occur, as well as the 2nd overtone . The
frequencies of the 1st and 2nd overtones provides information about the potential surface and about two to three
times that of the fundamental frequency

3.

For a diatomic, since is known, measurement of ue provides a value for k, the force constant.
where k is the force constant and indicates the strength of a bond.

Influence Factors of IR

Isotope Effects: It's been observed that the effect on k when an atom is replaced by an isotope is negligible but

it does have an effect on due to changes in the new mass. This is because the reduced mass has an effect on
the rotational and vibrational behavior.
Solvent Effects: The polarity of solvent will have an influence on the IR spectra of organic compounds due to the
interactions between solvent and compounds, which is called solvent effects. If we place a compound, which
contains n, pi and pi* orbitals, into a polar solvent, the solvent will stabilizes these three orbitals in different
extent. The stabilization effects of polar solvent on n orbital is the largest one, the next larger one is pi* orbital,
and the effects on pi orbital is the smallest one. The spectra of npi* transition will shift to blue side, which
means it will move to shorter wavelengths and higher energies since the polar solvent causes the energy
difference between n orbital and pi* orbital to become bigger. The spectra of pipi* transition will shift to red
side, which means it will move to longer wavelengths and lower energies since the polar solvent causes the
energy difference between n orbital and pi* orbital to become smaller.

Advantages of IR

High Scan Speed: Infrared spectroscopy can get information for the whole range of frequency simultaneously,

within one second. Therefore, IR can be used to analyze a substance that is not very stable and finish the scan
before it start to decompose.
High Resolution: The resolution of general prism spectrometer is only about 3 cm-1, but the resolution of
infrared spectrometer is much higher. For example, the resolution of Grating infrared spectrometer could be 0.2

cm-1, the resolution of FT infrared spectrometer could be 0.1-0.005 cm-1.

High Sensitivity: With Fourier Transform, the infrared spectrometer doesn't need to use the slit and
monochromator. In this way, the reflection specularity will be increased and the loss of energy in the analysis
process will be decreased. Therefore the energy that reaches the detector is large enough and even very small

amount of analytes could be detected. Nowadays, the infrared spectroscopy could detect the sample as small as
1-10 grams.
Wide Range of Application: Infrared spectroscopy could be used to analyze almost all organic compounds and
some inorganic compounds. It has a wide range of application in both qualitative analysis and quantitative

analysis. Also, the sample of Infrared spectroscopy doesn't have phase constraints. It could be gas, liquid or
solid, which has enlarged the range of analytes a lot.
Large Amount of Information: Infrared Spectra could give us lots of structural information of the analytes, such
as the type of compound, the functional group of compound, the stereoscopic structure of compound, the number

and position of substituent group and so on. Depending on the available information form the functional part and
the fingerprint part, infrared spectroscopy has become a great method to identify different kinds of compounds.
Non-Destructive: Infrared Spectroscopy is non-destructive to the sample.

Disadvantages of IR

Sample Constraint: Infrared spectroscopy is not applicable to the sample that contains water since the

hydroxide radical of the water molecule will introduce some disturbance to the measurement.
Spectrum Complication: The IR spectrum is very complicated and the interpretation depends on lots of
experience. Sometimes we cannot definitely clarify the structure of the compound just based on one single IR
spectrum. Other spectroscopy methods, such as ( Mass Spectrometry) MS and ( Nuclear Magnetic Resonance)

NMR, are still needed to further interpret the specific structure.

Quantification: Infrared spectroscopy works well for the qualitative analysis of a large variety of samples, but
quantitative analysis may be limited under certain conditions such as very high and low concerntrations.

Symmetry & IR Spectroscopy

One of the most importance applications of IR spectroscopy is structural assignment of the molecule depending
on the relationship between the molecule and observed IR absorption bands. Every molecule is corresponding to
one particular symmetry point group. Then we can predict which point group the molecule is belonging to if we
know its IR vibrational bands. Vice versa, we can also find out the IR active bands from the spectrum of the
molecule if we know its symmetry. These are two main applications of group theory. We'll take the following
problem as an example to illustrate how this works.

Question
How do you distinguish whether the structure of transition metal complex molecule M(CO) 2L4 is cis or trans by
inspection of the CO stretching region of the IR spectra?

Answer
For cis-M(CO)2L4, the symmetry point group of this molecule is C2v.
C2v

C2

(xz)

(yz)

co

co = A1 + B1
Since A1 has a basis on z axis and B1 has a basis on x axis, there are two IR vibrational bands observed in the
spectrum.
For trans-M(CO)2L4, the symmetry point group of this molecule is D4h.
D4h

C4

C2

C2'

C2"

S4

co

co = A1g + A2u
Since A2u has a basis on z axis, there is only one IR vibrational band observed in the spectrum.
Therefore, from what have been discussed above, we can distinguish these two structures based on the number
of IR bands.

Problems
The frequency of C=O stretching is higher than that of C=C stretching. The Intensity of C=O stretching is stronger
than that of C=C stretching. Explain it.

References
1.

D. A. Skoog, F. J. Holler, S. R. Crouch. Principles of Instrumental Analysis, 6th ed. Belmont, CA. Thomson

2.

Higher Education. 2007

G. D. Christain. Analytical Chemistry, 5th ed. New York. John Wiley & Sons, INC. 1994

3.

R. S. Drago. Physical Methods, 2nd ed. Mexico.Saunders College Publishing.1992

4.
5.

S.M. Blinder. Introduction to Quantum Mechanics. Academic Press. 2004

D. C. Harris, M. D. Bertolucci. Symmetry and Spectroscopy: An Introduction to Vibrational and Electronic
Spectroscopy. New York. Dover Publications, INC

Outside Links

http://en.wikipedia.org/wiki/Infrared_spectroscopy
http://en.wikipedia.org/wiki/Kinetic_isotope_effect
http://en.wikipedia.org/wiki/Solvent_effects
http://hyperphysics.phy-astr.gsu.edu/hbase/mod3.html

Contributors

Richard Osibanjo, Rachael Curtis, Zijuan Lai

How an FTIR Spectrometer Operates

FTIR spectrometers (Fourier Transform Infrared Spectrometer) are widely used in organic synthesis, polymer
science, petrochemical engineering, pharmaceutical industry and food analysis. In addition, since FTIR
spectrometers can be hyphenated to chromatography, the mechanism of chemical reactions and the detection of
unstable substances can be investigated with such instruments.

Introduction
The range of Infrared region is 12800 ~ 10 cm-1and can be divided into near-infrared region (12800 ~ 4000 cm-1),
mid-infrared region (4000 ~ 200 cm-1) and far-infrared region (50 ~ 1000 cm-1). The discovery of infrared light can
be dated back to the 19th century. Since then, scientists have established various ways to utilize infrared light.
Infrared absorption spectroscopy is the method which scientists use to determine the structures of molecules with
the molecules characteristic absorption of infrared radiation. Infrared spectrum is molecular vibrational spectrum.
When exposed to infrared radiation, sample molecules selectively absorb radiation of specific wavelengths which
causes the change of dipole moment of sample molecules. Consequently, the vibrational energy levels of sample
molecules transfer from ground state to excited state. The frequency of the absorption peak is determined by the
vibrational energy gap. The number of absorption peaks is related to the number of vibrational freedom of the
molecule. The intensity of absorption peaks is related to the change of dipole moment and the possibility of the
transition of energy levels. Therefore, by analyzing the infrared spectrum, one can readily obtain abundant
structure information of a molecule. Most molecules are infrared active except for several homonuclear diatomic
molecules such as O2, N2 and Cl2 due to the zero dipole change in the vibration and rotation of these molecules.
What makes infrared absorption spectroscopy even more useful is the fact that it is capable to analyze all gas,
liquid and solid samples. The common used region for infrared absorption spectroscopy is 4000 ~ 400 cm1
because the absorption radiation of most organic compounds and inorganic ions is within this region.
FTIR spectrometers are the third generation infrared spectrometer. FTIR spectrometers have several prominent
advantages: (1) The signal-to-noise ratio of spectrum is significantly higher than the previous generation infrared
spectrometers. (2) The accuracy of wavenumber is high. The error is within the range of 0.01 cm -1. (3) The scan
time of all frequencies is short (approximately 1 s). (4) The resolution is extremely high (0.1 ~ 0.005 cm -1). (5) The
scan range is wide (1000 ~ 10 cm-1). (6) The interference from stray light is reduced. Due to these advantages,
FTIR Spectrometers have replaced dispersive IR spectrometers.

Development of IR Spectrometers
Up till FTIR spectrometers, there have been three generations of IR spectrometers.
1.

The first generation IR spectrometer was invented in late 1950s. It utilizes prism optical splitting system. The
prisms are made of NaCl. The requirement of the samples water content and particle size is extremely strict.
Further more, the scan range is narrow. Additionally, the repeatability is fairly poor. As a result, the first

2.

generation IR spectrometer is no longer in use.

The second generation IR spectrometer was introduced to the world in 1960s. It utilizes gratings as the
monochrometer. The performance of the second generation IR spectrometer is much better compared with IR
spectrometers with prism monochrometer, But there are still several prominent weaknesses such as low
sensitivity, low scan speed and poor wavelength accuracy which rendered it out of date after the invention of the
third generation IR spectrometer.

3.

The invention of the third generation IR spectrometer, Fourier transform infrared spectrometer, marked the
abdication of monochrometer and the prosperity of interferometer. With this replacement, IR spectrometers
became exceptionally powerful. Consequently, various applications of IR spectrometer have been realized.

Dispersive IR Spectrometers
To understand the powerfulness and usefulness of FTIR spectrometer, it is essential to have some background
information of dispersive IR Spectrometer. The basic components of a dispersive IR spectrometer include a
radiation source, monochromator, and detector. The common IR radiation sources are inert solids that are heated
electrically to promote thermal emission of radiation in the infrared region of the electromagnetic spectrum.
The monochromator is a device used to disperse or separate a broad spectrum of IR radiation into individual
narrow IR frequencies.
Generally, dispersive spectrometers have a double-beam design with two equivalent beams from the same
source passing through the sample and reference chambers as independent beams. These reference and
sample beams are alternately focused on the detector by making use of an optical chopper, such as, a sector
mirror. One beam will proceed, traveling through the sample, while the other beam will pass through a reference
species for analytical comparison of transmitted photon wavefront information.
After the incident radiation travels through the sample species, the emitted wavefront of radiation is dispersed by
a monochromator (gratings and slits) into its component frequencies. A combination of prisms or gratings with
variable-slit mechanisms, mirrors, and filters comprise the dispersive system. Narrower slits gives better
resolution by distinguishing more closely spaced frequencies of radiation and wider slits allow more light to reach
the detector and provide better system sensitivity. The emitted wavefront beam (analog spectral output) hits the
detector and generates an electrical signal as a response.
Detectors are devices that convert the analog spectral output into an electrical signal. These electrical signals are
further processed by the computer using mathematical algorithm to arrive at the final spectrum. The detectors
used in IR spectrometers can be classified as either photon/quantum detectors or thermal detectors.
It is the absorption of IR radiation by the sample, producing a change of IR radiation intensity, which gets
detected as an off-null signal (e.g. different from reference signal). This change is translated into the recorder
response through the actions of synchronous motors. Each frequency that passes through the sample is
measured individually by the detector which consequently slows the process of scanning the entire IR region. A
block diagram of a classic dispersive IR spectrometer is shown in Figure 1.

Figure 1. Simplified representation of a dispersive IR spectrometer.

FTIR Spectrometers
The Components of FTIR Spectrometers
A common FTIR spectrometer consists of a source, interferometer, sample compartment, detector, amplifier, A/D
convertor, and a computer. The source generates radiation which passes the sample through the interferometer
and reaches the detector. Then the signal is amplified and converted to digital signal by the amplifier and analogto-digital converter, respectively. Eventually, the signal is transferred to a computer in which Fourier transform is
carried out. Figure 2 is a block diagram of an FTIR spectrometer.

Figure 2. Block diagram of an FTIR spectrometer

The major difference between an FTIR spectrometer and a dispersive IR spectrometer is the Michelson
interferometer.

Michelson Interferometer
The Michelson interferometer, which is the core of FTIR spectrometers, is used to split one beam of light into two
so that the paths of the two beams are different. Then the Michelson interferometer recombines the two beams
and conducts them into the detector where the difference of the intensity of these two beams are measured as a
function of the difference of the paths. Figure 3 is a schematic of the Michelson Interferometer.

Figure 3. Schematic of the Michelson interferometer

A typical Michelson interferometer consists of two perpendicular mirrors and a beamsplitter. One of the mirror is a
stationary mirror and another one is a movable mirror. The beamsplitter is designed to transmit half of the light
and reflect half of the light. Subsequently, the transmitted light and the reflected light strike the stationary mirror
and the movable mirror, respectively. When reflected back by the mirrors, two beams of light recombine with
each other at the beamsplitter.
If the distances travelled by two beams are the same which means the distances between two mirrors and the
beamsplitter are the same, the situation is defined as zero path difference (ZPD). But imagine if the movable
mirror moves away from the beamsplitter, the light beam which strikes the movable mirror will travel a longer
distance than the light beam which strikes the stationary mirror. The distance which the movable mirror is away
from the ZPD is defined as the mirror displacement and is represented by . It is obvious that the extra distance
travelled by the light which strikes the movable mirror is 2. The extra distance is defined as the optical path
difference (OPD) and is represented by delta. Therefore,

=2
It is well established that when OPD is the multiples of the wavelength, constructive interference occurs because
crests overlap with crests, troughs with troughs. As a result, a maximum intensity signal is observed by the
detector. This situation can be described by the following equation:

=n

(n = 0,1,2,3...)
In contrast, when OPD is the half wavelength or half wavelength add multiples of wavelength, destructive
interference occurs because crests overlap with troughs. Consequently, a minimum intensity signal is observed
by the detector. This situation can be described by the following equation:

=(n+12)
(n = 0,1,2,3...)
These two situations are two extreme situations. If the OPD is neither n-fold wavelengths nor (n+1/2)-fold
wavelengths, the interference should be between constructive and destructive. So the intensity of the signal
should be between maximum and minimum. Since the mirror moves back and forth, the intensity of the signal
increases and decreases which gives rise to a cosine wave. The plot is defined as an interferogram. When
detecting the radiation of a broad band source rather than a single-wavelength source, a peak at ZPD is found in
the interferogram. At the other distance scanned, the signal decays quickly since the mirror moves back and
forth. Figure 4(a) shows an interferogram of a broad band source.

Fourier Transform of Interferogram to

Spectrum
The interferogram is a function of time and the values outputted by this function of time are said to make up the
time domain. The time domain is Fourier transformed to get a frequency domain, which is deconvoluted to
product a spectrum. Figure 4 shows the Fast Fourier transform from an interferogram of polychromatic light to its
spectrum.

(a)

Figure 4. (a) Interferogram of a monochromatic light; (b) its spectrum

(b)

The Fourier Transform

The first one who found that a spectrum and its interferogram are related via a Fourier transform was Lord
Rayleigh. He made the discover in 1892. But the first one who successfully converted an interferogram to its
spectrum was Fellgett who made the accomplishment after more than half a century. Fast Fourier transform
method on which the modern FTIR spectrometer based was introduced to the world by Cooley and Turkey in
1965. It has been applied widely to analytical methods such as infrared spectrometry, nuclear magnetic
resonance and mass spectrometry due to several prominent advantages which are listed in Table 1.

Table 1. Advantages of Fourier Transform over Continuous-Wave Spectrometry

Fourier transform, named after the French mathematician and physicist Jean Baptiste Joseph Fourier, is a
mathematical method to transform a function into a new function. The following equation is a common form of the
Fourier transform with unitary normalization constants:

F()=12f(t)eitdt
in which t is time, i is the square root of -1.

The following equation is another form of the Fourier transform(cosine transform) which applies to real, even
functions:

F()=12f(t)cos(2t)dt
The following equation shows how f(t) is related to F(v) via a Fourier transform:

f(t)=12F()cos(2t)d

An Alternative Explanation of the Fourier Transform

in FTIR Spectrometers
The math description of the Fourier transform can be tedious and confusing. An alternative explanation of the
Fourier transform in FTIR spectrometers is provided here before we jump into the math description to give you a
rough impression which may help you understand the math description.
The interferogram obtained is a plot of the intensity of signal versus OPD. A Fourier transform can be viewed as
the inversion of the independent variable of a function. Thus, Fourier transform of the interferogram can be
viewed as the inversion of OPD. The unit of OPD is centimeter, so the inversion of OPD has a unit of inverse
centimeters, cm-1. Inverse centimeters are also known as wavenumbers. After the Fourier transform, a plot of
intensity of signal versus wavenumber is produced. Such a plot is an IR spectrum. Although this explanation is
easy to understand, it is not perfectly rigorous.

Simplified Math Description of the Fourier

Transform in FTIR
The wave functions of the reflected and transmitted beams may be represented by the general form of:

E1=rtcEmcos(t2kx)
and

E1=rtcEmcos[t2k(x+d)]
Where

d is the path difference,

r = reflectance (amplitude) of the beam splitter,
t is the transmittance, and
c is the polarization constant.
The resultant wave function of their superposition at the detector is represented as:

E=E1+E2=2(rtcEm)cos(t2kx)cos(kd)
Where Em,, , and k are the amplitude, frequency and wave number of the IR radiation source.
The intensity (I) detected is the time average of E2 and is written as

I=4r2t2c2E2mcos2(t2kx)cos2(kd)
Since the time average of the first cosine term is just , then

I=2I(k)cos2(kd)
and

I(d)=I(k)[1+cos(2kd)]
where I(k) is a constant that depends only upon k and I(d) is the interferogram.
From I(d) we can get I(k) using Fourier transform as follows:

I(d)I()=km0I(k)cos(2kd)dk
Letting Km , we can write

I(k)=0[I(d)I()]cos(2kd)dd
The physically measured information recorded at the detector produces an interferogram, which provides
information about a response change over time within the mirror scan distance. Therefore, the interferogram
obtained at the detector is a time domain spectrum. This procedure involves sampling each position, which can
take a long time if the signal is small and the number of frequencies being sampled is large.
In terms of ordinary frequency, , the Fourier transform of this is given by (angular frequency

=s):

f()=f(t)ei2tdt
The inverse Fourier transform is given by:

f()=f(t)e+i2tdt
The interferogram is transformed into IR absorption spectrum (Figure 5) that is commonly recognizable with
absorption intensity or % transmittance plotted against the wavelength or wavenumber. The ratio of radiant power
transmitted by the sample (I) relative to the radiant power of incident light on the sample (I 0) results in quantity of
Transmittance, (T). Absorbance (A) is the logarithm to the base 10 of the reciprocal of the transmittance (T):

A=log101T=log10T=log10II0

Figure 5. IR spectrum of a sample

Hands-on Operation of an FTIR Spectrometer

Step 1: The

first step is sample preparation. The standard method to prepare solid sample for FTIR

spectrometer is to use KBr. About 2 mg of sample and 200 mg KBr are dried and ground. The particle size
should be unified and less than two micrometers. Then, the mixture is squeezed to form transparent pellets which
can be measured directly. For liquids with high boiling point or viscous solution, it can be added in between two
NaCl pellets. Then the sample is fixed in the cell by skews and measured. For volatile liquid sample, it is
dissolved in CS2 or CCl4 to form 10% solution. Then the solution is injected into a liquid cell for measurement.
Gas sample needs to be measured in a gas cell with two KBr windows on each side. The gas cell should first be
vacuumed. Then the sample can be introduced to the gas cell for measurement.

Step 2: The second step is getting a background spectrum by collecting an interferogram and its subsequent
conversion to frequency data by inverse Fourier transform. We obtain the background spectrum because the
solvent in which we place our sample will have traces of dissolved gases as well as solvent molecules that
contribute information that are not our sample. The background spectrum will contain information about the
species of gases and solvent molecules, which may then be subtracted away from our sample spectrum in order
to gain information about just the sample. Figure 6 shows an example of an FTIR background spectrum.

Figure 6. Background IR spectrum

The background spectrum also takes into account several other factors related to the instrument performance,
which includes information about the source, interferometer, detector, and the contribution of ambient water (note
the two irregular groups of lines at about 3600 cm 1 and about 1600 cm1 in Figure 6) and carbon dioxide (note
the doublet at 2360 cm1 and sharp spike at 667 cm1 inFigure 6) present in the optical bench.

Step 3: Next, we collect a single-beam spectrum of the sample, which will contain absorption bands from the
sample as well as the background (gaseous or solvent).

Step 4: The ratio between the single-beam sample spectrum and the single beam background spectrum gives
the spectrum of the sample (Figure 7).

Figure 7. Sample IR spectrum

Step 5: Data analysis is done by assigning the observed absorption frequency bands in the sample spectrum
to appropriate normal modes of vibrations in the molecules.

Portable FTIR Spectrometers

Despite of the powerfulness of traditional FTIR spectrometers, they are not suitable for real-time monitoring or
field use. So various portable FTIR spectrometers have been developed. Below are two examples.
Ahonen et al developed a portable, real-time FTIR spectrometer as a gas analyzer for industrial hygiene use. The
instrument consists of an operational keyboard, a control panel, signal and control processing electronics, an
interferometer, a heatable sample cell and a detector. All the components were packed into a cart. To minimize
the size of the instrument, the resolution of FTIR spectrometer was sacraficed. But it is good enough for the use
of industrial hygiene. The correlation coefficient of hygienic effect between the analyzer and adsorption tubes is
about 1 mg/m3.
Korb et al developed a portable FTIR spectrometer which only weighs about 12.5 kg so that it can be held by
hand. Moreover, the energy source of the instrument is battery so that the mobility is significantly enhanced.
Besides, the instrument can function well within the temperature range of 0 to 45 oC and the humidity range of 0
to 100%. Additionally, this instrument resists vibration. It works well in an operating helicopter. Consequently, this
instrument is excellent for the analysis of radiation from the surface and atmosphere of the Earth. The instrument
is also very stable. After a three-year operation, it did not lose optical alignment. The reduction of size was
implemented by a creative design of optical system and accessory components. Two KBr prisms were used to
constitute the interferometer cavity. Optical coatings replaced the mirrors and beam splitter in the interferometer.
The optical path is shortened with a much more compact packaging of components. A small, low energy
consuming interferometer drive was designed. It is also mass balanced to resist vibration. The common He-Ne
tube was replaced by a smaller laser diode.

References
1.

P.R. Griffiths, Science, 21, 1983, 297

2.

W.D. Perkins, "Fourier Transform-Infrared Spectroscopy. Part 1. Instrumentation. Topics in Chemical

Instrumentation. Ed. Frank A. Settle, Jr. Journal of Chemical Education, 63:1, January 1986: A5-A10.

3.

D.A. Skoog and J.J. Leary. Principles of Instrumental Analysis, 4th Ed., Harcourt Brace Jovanovich.
Philadelphia, PA, 1992. Chapter 12.

4.
5.
6.

F. Daniels, J.W. Williams, P. Bender, R.A. Alberty, C.D. Cornwell, J. E. Harriman. "Experimental Physical
Chemistry, 7th Ed., McGraw-Hill, New York, NY, 1970.
J.W. Cooley and J.W. Turkey, Math. Comp., 1965, 19, 9
A.G. Marshall, Acc. Chem. Res., 1985, 18, 316

7.
8.

A. R. Korb, P. Dybwad, W. Wadsworth, J. W. Salisbury, Applied Optics, 1996, 35, 1679

I. Ahonen, H. Riipinen, A. Roos, Analyst, 1996, 121, 1253

9. D. W. Ball, Field Guide to Spectroscopy, SPIE Publication, Bellingham, 2006

10. V. Saptari, Fourier-Transform Spectroscopy Instrumentation Engineering, SPIE Publication, Bellingham, 2003
11. P. R. Griffiths, J. A. de Haseth, Fourier Transform Infrared Spectrometry, Wiley, New York, 1986
12. B. C. Smith, Fundamentals of Fourier Transform Infrared Spectroscopy, CRC press, 1996
13. B. Stuart, Modern Infrared Spectroscopy, Wiley, New York, 1996
14. A. L. Smith, Applied Infrared Spectroscopy : Fundamentals, Techniques, and Analytical Problem-solving, Wiley,
New York, 1979
15. P. R. Griffiths, Chemical Infrared Fourier Transform Spectroscopy, Wiley, New York, 1975

Outside Links

LBL - http://infrared.als.lbl.gov/content/web-links
FT-IR Tutorial: http://www.fc.up.pt/pessoas/peter.eaton/tutorial/webCT/
The League of Light - http://www.oceanoptics.com/lol/
FTIR explained by Mike at ALS http://www.youtube.com/watch?v=6isp-G4XBB8&feature=related
Caltech intro to FTIR: http://mmrc.caltech.edu/FTIR/FTIRintro.pdf
Fourier Transform: Why and how does it
work? http://www.youtube.com/watch?v=ObklYbQaX24&NR=1&feature=fvwp

Contributors

Nancy Birkner (UCD), Qian Wang (UCD)

http://people.whitman.edu/~dunnivfm/C_MS_Ebook/CH6/6_14.html

6.14 Fragmentation of Esters

The molecular ion peak of straight chain esters is sometimes
discernable. A prevalent peak and often the base peak results from the
familiar McLafferty rearrangement. The size of the alcohol that formed the
ester and the presence of substituents can normally be discerned by the
mass of these two peaks. Esters also under go a cleavage of the bond to
the carbonyl group.

The cleavage of the above bonds results in other fragments, however these
peaks are too small to be of great significance. For example, hexanoic acid
methyl ester produces the following fragments.

The resonance stabilized acylium ion gives a discernable peak for almost
all esters. The R+ ion is prominent in short chain esters but is barely
visible in esters with more than six carbon atoms. For hexanoic acid
methyl ester, the R+ ion is only 9.5% of the base peak.
Until this point, this chapter has covered individual functional groups in
isolation. Since esters have both an alcohol and an acid component,
fractionation patterns can be observed from both of these types of
compounds. The prevalence of the fragments described earlier is
dependent on the size of each part of the ester. The increased size of
each portion results in a unique rearrangement.
When the acid portion is the major component like in hexanoic acid methyl
ester, the fractionation pattern is partially characterized by typical acid
peaks. For these straight chain esters, cleavage of successive carbon

atoms gives an alkyl fragment and a fragment containing oxygen. This

pattern results in the familiar grouping of fragments spaced 14 units apart
with the largest fragment in the cluster resulting from the CnH2n-1O2 ion
(Figure 6.19).

Figure 6.19. Fragmentation of an Ester. Spectra from the NIST/EPA/NIH

Mass Spectral Library. Reprinted with permission from NIST.
The base peak in Figure 6.19 is a result of the McLafferty
rearrangement.

When the alcohol portion of the ester is the prominent portion of the ester,
fragments similar to that of an alcohol are observed. These esters will lose
a molecule of acid like alcohols loose a molecule of water. In esters
formed from larger alcohols, the prevalence of this rearrangement is so
frequent that the molecular ion is normally absent from the spectra.

These types of esters will also lose the alkyl fragment from the
alcohol portion of the ester accompanied by two hydrogen migrations.

In aromatic esters, the molecular ion is prominent due to the aromatic

group. There are two distinctive types of aromatic esters that have their
own unique fractionation patterns. Esters synthesized from aromatic acids
mostly undergo cleavages.

The loss of OR results in the base peak because of the multiple resonance
forms stabilizing the cation. When the alkyl portion of the alcohol becomes
longer, the McLafferty rearrangement and the loss of R with two hydrogen
migrations explained above is more favorable. Increasing the size of the R
chain will cause the alkyl portion to retain the charge.

Esters synthesized from aromatic alcohols have a prominent peak at m/z

43 due to the CH3CO+ ion. These esters also undergo a rearrangement
that results in the loss of a ketene molecule.

Frank's Homepage

Infrared: Application
Infrared spectroscopy, an analytical technique that takes advantage of the vibrational transitions of a molecule,
has been of great significance to scientific researchers in many fields such as protein characterization, nanoscale
semiconductor analysis and space exploration.

Introduction
Infrared spectroscopy is the study of interaction of infrared light with matter, which can be used to identify
unknown materials, examine the quality of a sample or determine the amount of components in a mixture.
Infrared light refers to electromagnetic radiation with wavenumber ranging from 13000 10 cm-1 (corresponding
wavelength from 0.78 1000 m). Infrared region is further divided into three subregions: near-infrared (13000
4000 cm-1 or 0.78 2.5 m), mid-infrared (4000 400 cm-1 or 2.5 25 m) and far-infrared (400 10 cm-1 or 25
1000 m). The most commonly used is the middle infrared region, since molecules can absorb radiations in this
region to induce the vibrational excitation of functional groups. Recently, applications of near infrared
spectroscopy have also been developed.
By passing infrared light through a sample and measuring the absorption or transmittance of light at each
frequency, an infrared spectrum is obtained, with peaks corresponding to the frequency of absorbed radiation.
Since all groups have their characteristic vibrational frequencies, information regarding molecular structure can
be gained from the spectrum. Infrared spectroscopy is capable of analyzing samples in almost any phase (liquid,
solid, or gas), and can be used alone or in combination with other instruments following different sampling
procedures. Besides fundamental vibrational modes, other factors such as overtone and combination bands,
Fermi resonance, coupling and vibration-rotational bands also appear in the spectrum. Due to the high
information content of its spectrum, infrared spectroscopy has been a very common and useful tool for structure
elucidation and substance identification.

Instrumentation
Most commonly used instruments in infrared spectroscopy are dispersive infrared spectrometer and Fourier
transform infrared spectrometer.

Dispersive infrared spectrometer

Dispersive infrared spectrometer is mainly composed of radiation source, monochromator and detector. For midinfrared region, Globar (silicon carbide), Nernst glower (oxides of zirconium, yttrium and erbium) and metallic
helices (chromium-nickel alloy or tungsten) are frequently used as radiation sources. Tungsten-halogen lamps
and metallic conductors coated with ceramic are utilized as sources for near-infrared region. A mercury highpressure lamp is suitable for far-infrared region.
Monochromator in conjunction with slits, mirrors and filters separates the wavelengths of light emitted. The
dispersive elements within monochromator are prisms or gratings. Gratings have gradually replaced prisms due
to their comparatively low cost and good quality. As shown in Figure 1, radiation passes through both a sample
and a reference path. Then the beams are directed to a diffraction grating (splitter), which disperses the light into
component frequencies and directs each wavelength through a slit to the detector. The detector produces an
electrical signal and results in a recorder response.

Figure 1. Schematic illustration of dispersive infrared spectrometer. Figure from Wikipedia.

Two types of detectors are employed in dispersive infrared spectrometer, namely, thermal detectors and photon
detectors. Thermal detectors include thermocouples, thermistors, and pneumatic devices, which measure the
heating effect generated by infrared radiation. Photon detectors are semiconductor-based. Radiation is able to
promote electrons in photon detectors from valence band to conduction band, generating a small current. Photon
detectors have faster response and higher sensitivity than do thermal detectors but are more susceptible to
thermal noise.

Fourier transform infrared spectrometer

Dispersive infrared spectrometer has many limitations because it examines component frequencies individually,
resulting in slow speed and low sensitivity. Fourier transform infrared (FTIR) spectrometer is preferred over
dispersive spectrometer, since it is capable of handling all frequencies simultaneously with high throughput,
reducing the time required for analysis. The radiation sources used in dispersive infrared spectrometer can also
be used in FTIR spectrometer.
In contrast with the monochromator in dispersive spectrometer, FTIR spectrometer as shown in Figure
2 employs an interferometer. The beamsplitter within the interferometer splits the incoming infrared beam into two
beams, one of which is reflected by a fixed mirror, while the other one reflected by a moving mirror perpendicular
to the fixed one. The length of path one beam travels is fixed and that of the other one is changing as the mirror
moves, generating an optical path difference between the two beams. After meeting back at the beamsplitter,
the two beams recombine, interfere with each other, and yield an interferogram. The interferogram produces
inference signal as a function of optical path difference. It is converted to a spectrum of absorbance or
transmittance versus wavenumber or frequency by Fourier transform.

Figure 2. Schematic representation of Fourier transform infrared spectrometer. Figure from Wikipedia.
Detectors used in FTIR spectrometers are mainly pyroelectric and photoconductive detectors. The former are
constructed of crystalline materials (such as deuterated triglycine sulfate) whose electric polarization rely on
temperature. The change in temperature leads to change in charge distribution of the detector and electric signal
is produced. The latter (such as mercury cadmium telluride) provide better sensitivity and faster speed than do
pyroelectric detectors over a broad spectral range. However, liquid nitrogen is needed for cooling of
photoconductive detectors.

Application
Since different molecules with different combination of atoms produce their unique spectra, infrared spectroscopy
can be used to qualitatively identify substances. In addition, the intensity of the peaks in the spectrum is
proportional to the amount of substance present, enabling its application for quantitative analysis.

Qualitative analysis
For qualitative identification purposes, the spectrum is commonly presented as transmittance versus
wavenumber. Functional groups have their characteristic fundamental vibrations which give rise to absorption at
certain frequency range in the spectrum (Figure 3).

Figure 3.Infrared spectrum of 1-hexanol.

Each band in a spectrum can be attributed to stretching or bending mode of a bond. Almost all the fundamental
vibrations appear in the mid-infrared region. For instance, 4000 2500 cm-1 region usually can be assigned to
stretching modes of O-H, N-H or C-H. Triple-bond stretching modes appear in the region of 2500 2000 cm-1.
C=C and C=O stretching bands fall in the 2000 1500 cm-1 region. Hence, characterization of functional groups
in substances according to the frequencies and intensities of absorption peaks is feasible, and also structures of
molecules can be proposed. This method is applicable to organic molecules, inorganic molecules, polymers, etc.
A detailed frequency list of functional groups is shown in Figure 4. Note that several functional groups may
absorb at the same frequency range, and a functional group may have multiple-characteristic absorption peaks,
especially for 1500 650 cm-1, which is called the fingerprint region.

Figure 4. Characteristic infrared absorption frequencies.

Bands in the near-infrared region are overtones or combination bands. They are weak in intensity and
overlapped, making them not as useful for qualitative analysis as those in mid-infrared region. However,
absorptions in this region are helpful in exploiting information related to vibrations of molecules containing heavy
atoms, molecular skeleton vibrations, molecular torsions and crystal lattice vibrations.
Besides structural elucidation, another qualitative application of infrared spectroscopy is the identification of a
compound with a reference infrared spectrum. If all the peaks of the unknown match those of the reference, the
compound can be identified. Additional reference spectra are available online at databases such as NIST
Chemistry WebBook.

Quantitative analysis
Absorbance is used for quantitative analysis due to its linear dependence on concentration. Given by BeerLambert law, absorbance is directly proportional to the concentration and pathlength of sample:

A=cl
where A is absorbance, the molar extinction coefficient or molar absorptivity which is characteristic for a specific
substance, c the concentration and l the pathlength (or the thickness) of sample. The conversion from
transmittance to absorbance is given by

A=logT
where T is transmittance.

For quantitative analysis of liquid samples, usually an isolated peak with high molar absorptivity that appears in
the spectrum of the compound is chosen. A calibration curve of absorbance at the chosen frequency against
concentration of the compound is acquired by measuring the absorbance of a series of standard compound
solution with known concentrations. These data are then graphed to get a linear plot, from which the
concentration of the unknown can be calculated after measuring its absorbance at the same frequency. The
number of functional groups can also be calculated in this way, since the molar absorptivity of the band is
proportional to the number of functional groups that are present in the compound.
For solid samples, an internal standard with a constant known amount is added to the unknown sample and the
standards. Then similar procedures as those with liquid samples are carried out except that the calibration curve
is a graph of the ratio of absorbance of analyte to that of the internal standard versus concentration of the
analyte.
A multi-component analysis of the mixture is also feasible since different components have different values of
molar absorptivity at the same frequency.
However, infrared spectroscopy may be more susceptible to deviation from Beer's law than is UV-Vis
spectroscopy because of its narrow bands, complex spectra, weak incident beam, low transducer sensitivity and
solvent absorption.

Reference
1.

Settle, F. A. Handbook of instrumental techniques for analytical chemistry; Prentice Hall PTR: Upper Saddle
River, NJ, 1997.

2.
3.

Heigl, J. J.; Bell, M.; White, J. U. Anal. Chem. 1947, 19, 293.
Baker, A. W. J. Phys. Chem. 1957, 61, 450.

4.

Kamariotis, A.; Boyarkin, O. V.; Mercier, S. R.; Beck, R. D.; Bush, M. F.; Williams, E. R.; Rizzo, T. R. J. Am.
Chem. Soc. 2006, 128, 905.

5.
6.

Stuart, B. Infrared spectroscopy fundamentals and applications; J. Wiley: Chichester, Eng.; Hoboken, N.J., 2004.
Gnzler, H.; Heise, H. M. IR spectroscopy: an introduction; Wiley-VCH: Weinheim, 2002.

7.

Wartewig, S. IR and Raman spectroscopy: fundamental processin; Wiley-VCH: Weinheim, 2003.

Outside Links

NIST Chemistry WebBook: http://webbook.nist.gov/

Wikipedia: http://en.wikipedia.org/wiki/Infrared_spectroscopy

Contributor

Xixuan Li (UC Davis)