Electronic transitions involves transfer of one

electron from one orbital to another

Radiation source: UV vis photons

Vibrational and rotational transitions occurs with

polyatomic species since molecules have a
multitude of quantized energy levels (or vibrational
states) associated with the bonds that hold the
molecule together

Variations in rotational levels may also give rise to a

series of peaks for each vibrational state; with
liquid or solid samples, however, rotation is often
hindered or prevented and the effects of these
small energy differences are not detected.

E = E electronic + E vibrational + E rotational

Ground state of an atom or a molecular species:

Minimum energy state of the species
 Infrared Spectroscopy
based on IR absorption by molecules as undergo vibrational and rotational transitions.
rotational transitions
Potential Energy (E)

Vibrational transitions

Potential energy resembles classic Harmonic Oscillator

Interatomic Distance (r)
Theory of Infrared Absorption Spectroscopy

• In order for IR absorbance to occur two conditions must be met:

1. There must be a change in the dipole moment of the molecule as a

result of a molecular vibration (or rotation). The change (or
oscillation) in the dipole moment allows interaction with the
alternating electrical component of the IR radiation wave.
Symmetric molecules (or bonds) do not absorb IR radiation since
there is no dipole moment.

2. If the frequency of the radiation matches the natural frequency of

the vibration (or rotation), the IR photon is absorbed and the
amplitude of the vibration increases.
DE = hn
• There are three types of molecular transitions that occur in IR
a) Rotational transitions
• When an asymmetric molecule rotates about its center of mass, the
dipole moment seems to fluctuate.
• DE for these transitions correspond to n < 100 cm-1
• Quite low energy, show up as sharp lines that subdivide vibrational
peaks in gas phase spectra.
b) Vibrational-rotational transitions
• complex transitions that arise from changes in the molecular dipole
moment due to the combination of a bond vibration and molecular
rotation.
c) Vibrational transitions
• The most important transitions observed in qualitative mid-IR
spectroscopy.
• n = 13,000 – 675 cm-1 (0.78 – 15 µM)
 Mechanical Model of Stretching Vibrations
1. Simple harmonic oscillator.
• Hooke’s Law (restoring force of a spring is proportional to the
displacement)

F = -ky

Where: F = Force
k = Force Constant
(stiffness of spring)
y = Displacement

• Natural oscillation frequency of a mechanical oscillator depends on:

a) mass of the object
b) force constant of the spring (bond)
• The oscillation frequency is independent of the amount of energy
imparted to the spring.
• Frequency of absorption of radiation can be predicted with a modified
Hooke’s Law.

Where: n = wavenumber of the abs. peak (cm-1)

1
1 ækö 2 c = speed of light (3 x 1010 cm/s)
n = çç ÷÷ k = force constant
2pc è µ ø
µ = reduced mass of the atoms

Mx •My Where: Mx = mass of atom x in kg

µ=
Mx + My My = mass of atom y in kg

• Force constants are expressed in N/m (N = kg•m/s2)

- Range from 3 x 102 to 8 x 102 N/m for single bonds
- 500 N/m is a good average force constant for single bonds when
predicting k.
- k = n(500 N/m) for multiple bonds where n is the bond order
 ii.) Anharmonic oscillation:
- harmonic oscillation model good at low energy levels (n0, n1, n2, …)
- not good at high energy levels due to atomic repulsion & attraction
• as atoms approach, coulombic repulsion force adds to the bond
force making energy increase greater then harmonic
• as atoms separate, approach dissociation energy and the harmonic
function rises quicker

Harmonic oscillation

Anharmonic oscillation

Because of anharmonics: at low DE, Dn =±2, ±3 are observed which cause the appearance of
overtone lines at frequencies at ~ 2-3 times the fundamental frequency. Normally Dn = ± 1
iii.) Types of Molecular Vibrations

Bond Stretching Bond Bending

symmetric In-plane rocking

asymmetric In-plane scissoring

Out-of-plane wagging

Out-of-plane twisting
 symmetric asymmetric In-plane scissoring

Out-of-plane twisting In-plane rocking Out-of-plane wagging

Another Illustration of Molecular Vibrations
iv.) Number of Vibrational Modes:
- for non-linear molecules, number of types of vibrations: 3N-6
- for linear molecules, number of types of vibrations: 3N-5
- why so many peaks in IR spectra
- observed vibration can be less then predicted because
• symmetry ( no change in dipole)
• energies of vibration are identical
• absorption intensity too low
• frequency beyond range of instrument

Examples:
1) HCl: 3(2)-5 = 1 mode

2) CO2: 3(3)-5 = 4 modes

- + - moving in-out of plane

See web site for 3D animations of vibrational modes for a variety of molecules
http://www.chem.purdue.edu/gchelp/vibs/co2.html
v.) IR Active Vibrations:
- In order for molecule to absorb IR radiation:
• vibration at same frequency as in light
• but also, must have a change in its net dipole moment
as a result of the vibration

Examples:
1) CO2: 3(3)-5 = 4 modes µ = 0; IR inactive
d- 2d+ d-
µ > 0; IR active
d- 2d+ d-
- + - µ > 0; IR active
d- 2d+ d-
degenerate –identical energy single IR peak
2d+
µ > 0; IR active
d- d-
IR spectrum of CO2
10. Infrared Absorption Signals

Selected IR frequencies.11

The vibrational frequencies of certain functional groups will correspond to the absorption of certain
Alkanes
Alkenes vs. Alkanes
 Alkynes Alkynes contain the C≡C structural unit, properly called a carbon-carbon triple bond.

In the IR spectrum of a disubstituted alkyne only the peak B (ca. 2100 cm-1) is present. The band at ca. 3300 cm-1 and 630
cm-1 together are fingerprints of terminal (monosubstituted) alkynes
 Ether
Since all ethers contain a C-O-C linkage, the
vibration that we would usually refer to as a “C-O”
stretch actually involves the asymmetric stretch of
the C-O-C
This vibration is analogous to the C-C-O
asymmetric stretch of alcohols, and like alcohols
these peaks are typically the largest ones found
between 1300 and 1000 cm-1
The C-O-C linkage can also undergo a symmetric
stretch.
This peak is typically not as intense as the C-O-C
asymmetric stretch because du/dx for the symmetric
stretch is less than that for the asymmetric stretch.
This peak typically falls between 890 and 820 cm-1.
Aliphatic ether

C-O-C symm stretch

C-O-C asymm stretch

This C-C-O asymmetric stretch is at 1238 cm-1 and is labeled A.
For aromatic ethers, in general, this peak falls between 1300
and 1200 cm-1.
Two C-O stretch:
#1 the aromatic C-O stretch as being at 1247 cm-1, which is labeled A in the figure
#2 the saturated C-O stretch as being at 1040 cm-1, which is labeled B

NOTE:

the symmetric C-H stretch for a

methoxy group falls at 2830 ± 10 cm-1,
whereas for a CH3-C group it falls at
2872 ± 10 cm-1.
Note that this peak is sharp, of
medium intensity, and a little lower in
wavenumber than most C-H stretches.
These unique features make the
methoxy C-H symmetric stretch an
excellent group wavenumber, and the
best indication in a spectrum that a
methoxy group is present in a sample.
Ether
 Alcohol

broad, strong O-H stretch at 3350 ± 50 cm-1

All types of alcohols are characterized by the same OH, vibrational mode (labelled as
A and G in the spectrum). To distinguish between primary alcohols and secondary or
tertiary, look at the position of the C-O asymm stretch!
* For primary alcohol C-C-O asymmetric strectching between 1000 and 1075 cm-1
 The carbonyl or C=O group is the perfect functional group for detection by
infrared (IR) spectroscopy because its stretching vibration peak is intense and is
located in a unique wavenumber range.

These bonds are very common and are found in ketones, aldehydes, esters, and
carboxylic acids, among others. The types of materials where you will find
carbonyl groups include polymers, proteins, fats, solvents, and pharmaceuticals.

Carbonyl bonds are highly polar because of the large electronegativity

difference between carbon and oxygen. As a result, the carbonyl carbon
C=O stretching
has a large partial positive charge and the oxygen has a large partial
negative charge.
Remember that one of the characteristics that determines the intensity of
infrared peaks is the change in dipole moment with respect to bond
length, dµ/dx, during a molecular vibration.
Since the carbonyl group has a large dipole moment, when this group Carbonyl stretching region: 1900 and 1600 cm-1
stretches and contracts the value of dµ/dx is large, thereby giving an (a relatively unique part of the IR spectrum)
intense peak.
Saturated carbonyl
C=O In general, for saturated carbonyl (aldeheyde,
stretching ketones, ester, carboxylic acid) this peak
appears at 1715 ± 10 cm-1.
Aromatic carbonyl aromatic C=O stretching peaks fall ~30 cm-1 lower than saturated C=O stretching peaks.

C=O
stretching
 Carbonyl group: KETONES
The peak that can help distinguish them from other functional groups is the C-C-C stretch vibration.
Note that this vibration involves the two alpha carbons stretching asymmetrically about the
carbonyl carbon.
This vibration gives rise to an intense peak between 1230 and 1100 cm-1 for saturated ketones.
Carbonyl group: KETONES Normally a C-C stretching vibration peak is small since the electronegativity difference
between two carbon atoms is often negligible, giving nonpolar bonds and small values of
dµ/dx.
However, the carbonyl carbon in the C=O bond has a large positive partial charge on it. This
charge polarizes the bonds to the two alpha carbons, and when these C-C bonds stretch
dµ/dx is large, giving the typically large ketone C-C-C stretching peak labeled B in Figure
Aromatic ketones
For aromatic ketones, generally
the C-C-C stretch falls between
C=O 1300 and 1230 cm-1.
stretching
Carbonyl group: KETONES
 Methyl Ketones and Their Umbrella Mode

The methyl groups in acetone and acetophenone also exhibit an umbrella mode at 1362 cm-1 and 1360 cm-1, respectively.
This intense CH3 umbrella mode is indicative of a methyl ketone. Thus, if your analysis of a spectrum indicates that a ketone
and methyl group are present, and the CH3 umbrella mode is unusually large, problably you have a methyl ketone. This peak
is diagnostically very useful.
After a ketone is identified the next step is to determine the two substituents attached to the carbonyl carbon. The large
methyl ketone umbrella mode tells us that one of the substituents is a CH3 group.
NOTE: find the umbrella mode in previous and following spectra
The C=O Bond: Aldehydes These molecules feature a unique "lone hydrogen" atom giving rise to
unique C-H stretching and bending peaks, making aldehydes easy to spot.

Because the oxygen in the C=O bond is very electronegative, it pulls

electron density away from the aldehydic C-H bond, weakening the bond
and lowering its force constant. The net effect is a lowering of the aldehydic
C-H stretch to the 2850–2700 cm-1 range.
This is one of the lowest wavenumber C-H stretches you will ever see.

For aldehydes the combination of a low wavenumber C-H stretch and a C=O stretch are diagnostic.
The carboxylic acids These molecules have C=O, C-O, and O-H bonds, giving them a number of
diagnostically useful group wavenumbers and making this functional group easy to
spot. We also see how the spectra of saturated and aromatic carboxylic acids differ
from each other.

WORTH NOTING:

The one characteristic that determines peak widths in IR spectra is the strength of
intermolecular bonding. Briefly, weak intermolecular interactions give narrow peaks
while strong intermolecular interactions give broad peaks. Thus, when the IR
spectra of solid and liquid carboxylic acids are measured it is the spectrum of the
dimer that is actually seen. Not surprisingly then, the IR peaks of carboxylic acids
are unusually broad
- O-H stretch (labeled A): so broad that there isn't
really a peak position for it, just a range in which
this wide envelope falls, from 3500 to 2500 cm-1.

- C-H stretches (from the methyl and methylene

groups in this molecule): narrow peaks that fall on
top of the much broader O-H stretching envelope.
It's not unusual in IR spectra for narrow peaks to
show up on top of or as a shoulder on broader
peaks when both happen to fall in the same
wavenumber range such as this. This spectral
region is another example of how peak widths can
be used to distinguish functional groups from each
other, with the nonpolar C-H bond stretches being
much narrower than the polar O-H stretch.

O-H wagging: lke alcohol, carboxylic acids also have

a wagging peak generally found from 960 to 900
cm-1 (here at 942 cm-1, labeled F). Note how broad
this peak is because of hydrogen bonding. There
are very few other functional groups that have
broad peaks around 900 cm-1, making this peak
diagnostically useful.
 - C=O stretch: in general for saturated carboxylic acids
this peak falls from 1730 to 1700 cm-1.
Note that the C=O stretches of saturated ketones and
aldehydes also fall in this range. Thus, as has been
pointed out before, the position of carbonyl stretches
by themselves is not enough to identify specific C=O
containing functional groups, other peaks will be
needed.
In the case of carboxylic acids, it is the combination of
a broad -OH stretch and a C=O stretching peak that
gives us a diagnostically useful pattern. Other
molecules, such as water and alcohols, have broad OH
stretching peaks but no C=O peak.

- asymm C-O stretching: for carboxylic acids this peak

appears between 1320 and 1210 cm-1 (in the figure it
falls at 1230 cm-1, labeled E). , which is within the
general range from 1300 to 1000 cm-1.

intense diagnostically useful peaks: the OH stretch, C=O stretch, C-O stretch, and OH wag
The highly polar nature of the carboxylic acid groups
causes many peaks to appear with more intensity
than they would in a less polar molecule because of
large values of dµ/dx.

The first thing that should stand out is the broad

envelope labeled A that extends from 3500 to 2000;
it makes up almost half the spectrum and is one of
the broadest IR peaks you will ever see! This is of
course the OH stretch of the carboxylic acid
functional group.
The C-H stretching peak of the aromatic ring is a
sharp shoulder at 3071.
There are overtone and combination bands in the
2800 to 2500 neighborhood labeled B.
The C=O stretch of benzoic acid is at 1685, and in
general for aromatic carboxylic acids this peak falls
from 1710 to 1680, lower than for saturated acids,
because of conjugation. The C-O stretch of benzoic
acid is at 1292, and the O-H wag at 934, which is in
line with the peak positions quoted above. Note that
the only peak position here sensitive to whether a
carboxylic acid is saturated or aromatic is the C=O
stretch.
Esters Esters are a common and economically important functional group made by reacting an alcohol
and a carboxylic acid. Their structural framework consists of a C=O group and two C-O bonds. This
gives rise to three intense peaks called the Rule of Three with peak positions at approximately
1700, 1200, and 1100 wavenumbers. The three vibrations involved are the C=O stretch, a C-C-O
stretch, and an O-C-C stretch.
Note that ester groups contain one C=O bond
and two C-O bonds.
So we can take a stab at predicting what their
spectra might look like.
- carbonyl stretching peaks are strong and
generally occur between 1800 and 1600 cm-1
- C-O stretches are intense peaks typically seen
between 1300 and 1000. Since one of the C-
O bonds in the ester group is attached to the
carbonyl carbon and the other is not, we
might expect the two to be chemically
distinct, have different force constants, and
hence give rise to two separate peaks
between 1300 and 1000.
NITRILE (-CN)

In a manner very similar to alkynes, nitriles show a prominent band around 2250 cm-1 caused by the CN triple
bond. This band has a sharp, pointed shape just like the alkyne C-C triple bond, but because the CN triple bond
is more polar, this band is stronger than in alkynes.
AMIDES (-CO-NH-)

The amide functional group combines the features of amines and ketones because it has both the N-H bond and
the C=O bond. Therefore amides show a very strong, somewhat broad band at the left end of the spectrum, in
the range between 3100 and 3500 cm-1 for the N-H stretch. At the same time they also show the stake-shaped
band in the middle of the spectrum around 1710 cm-1 for the C=O stretch. As with amines, primary amides show
two spikes, whereas secondary amides show only one spike.
 Alkyl Halide (C-X, with X: F, Cl, Br, I)

Alkyl halides are compounds that have a C–X bond, where X is a halogen: bromine, chlorine, fluorine, or iodine
(usually Br or Cl in the organic chemistry teaching labs).
In general, C–X vibration frequencies appear in the region 850-515 cm-1, sometimes out of the range of typical IR
instrumentation. C–Cl stretches appear from 850–550 cm-1, while C–Br stretches appear at slightly lower
wavenumbers from 690-515 cm-1. In terminal alkyl halides, the C–H wag of the –CH2X group is seen from 1300-
1150 cm-1. Complicating the spectra is a profusion of absorptions throughout the region 1250-770 cm-1, especially
in the smaller alkyl halides. Note that all of these bands are in the fingerprint region.

In summary, the following bands are specific to alkyl halides:

• C–H wag (-CH2X) from 1300-1150 cm-1

• C–X stretches (general) from 850-515 cm-1
• C–Cl stretch 850-550 cm-1
• C–Br stretch 690-515 cm-1