The interactions of radiation and matter are the subject of the science called spectroscopy

Radiation is the emission or transmission of Matter is a substance that has mass and takes
energy in the form of wave or particles up space, and is made up of particles.
through space or a medium.

1. Electromagnetic radiation consists of photons, Electromagnetic radiation is a form of energy that is

such as radio waves, microwaves, infrared, transmitted through space at enormous velocities.
visible light, ultraviolet, X-rays, and gamma
rays (γ).
2. Particle radiation consist of particles of non- Electromagnetic radiation can be described as a wave
zero rest energy, such as alpha radiation (α), with properties of wavelength, frequency, velocity, and
beta radiation (β), proton radiation and neutron amplitude. In contrast to sound waves, light requires no
radiation. transmitting medium; thus, it can travel readily through a
3. Acoustic radiation, such as ultrasound, sound, vacuum. Light also travels nearly a million times faster
and seismic wave, dependent on a physical than sound.
transmission medium.
The wave model fails to account for phenomena associated with the absorption and emission of radiant energy.
For these processes, electromagnetic radiation can be treated as discrete packets of energy or particles called
photons or quanta. These dual views of radiation as particles and waves are not mutually exclusive but
complementary.

The frequency () is the number of oscillations of the

electric field vector per unit time. Its unit is s-1 or Hz.
The frequency of a light wave or any wave of
electromagnetic radiation is determined by the source
that emits it and remains constant regardless of the
medium traversed.
The wavelength () is the linear distance between
successive maxima or minima of a wave and its unit is
m.
the velocity (v) is the speed at which a wave moves
through a medium. Its unit is ms-1.
A wavenumber (ṽ) is the number of waves in a unit
distance. It's measured in radians or cycles per unit
distance. .
𝑣 = 𝜆𝜈
In a vacuum, light travels at its maximum velocity. This velocity, which is
given the special symbol c, is 2.99792 x 108 m s-1. The velocity of light in
air is only about 0.03 % less than its velocity in vacuum.
𝑐 = 𝜆𝜈
Electromagnetic radiations consists of particles
having small packets of energies called quanta or
photons.
Photons possess the characteristic of wave and
travel with the speed of light.
The amount of energy corresponding to one photon
is expressed by Planck’s equation as

𝐸 = ℎ𝜈
h = Planck’s constant (6.62x10-34 Js)

A short wavelength means that the frequency will

be higher and a longer wavelength has a lower
frequency.
 Interaction of EMR with matter
EMR interacts with matter only when the matter has some electric and magnetic effect and are influenced by the
electric and magnetic components of the EM radiation.
The electromagnetic spectrum covers an enormous range of energies (frequencies) and thus wavelengths
The net change in the electric/magnetic dipole moment in the molecule or nuclear spin, interact with the
magnetic/electrical component of the EMR by either absorption or emission of the EMR.
Total energy of molecules = Translational + Rotational + Vibrational + Electronic
➢ Absorption or emission of EMR causes a change in any of these types of energies.
➢ In molecular spectroscopy, we measure the change in these energy states.

Translational Energy
➢ It is due to the overall movement of the molecule.
➢ Energy levels are not quantized.
➢ Hence no spectroscopy.

Vibrational Energy
➢ It is due to vibrations in molecules
➢ Vibrational Levels are Quantized
➢ IR Spectroscopy (Vibrational spectroscopy)

Rotational energy
➢ It is due to spinning of molecules about the axis passing through the centre of gravity
➢ Rotational Levels are quantized
➢ Rotational spectroscopy (Microwave spectroscopy)
Electronic energy
➢ Consists of electronic levels which are quantized
➢ UV/visible spectroscopy (Electronic spectroscopy)
Spectra
➢ Molecular spectra result from either the absorption or the
emission of electromagnetic radiation as molecules undergo
changes from one quantized energy state to another.
➢ Molecules are not rigid structures, and the motion of the
nuclei within the molecular framework gives rise to
vibrational energy levels.
➢ In the gas phase, where they are widely separated relative to
their size, molecules can undergo free rotation and as a
result possess quantized amounts of rotational energy.
➢ In theory, the translational energy of molecules through
space is also quantized, but in practice the quantum effects
are so small that they are not observable, and the motion
appears continuous.
➢ The interaction of electromagnetic radiation with these
molecular energy levels constitutes the basis for Electronic,
IR and Microwave spectroscopy.
Absorption and Emission Spectra
➢ Absorption of electromagnetic radiation by compounds gives
absorption spectrum and spectrum obtained by the emission of
absorbed radiation is called emission spectrum.
➢ Ground level/state is the lowest energy state.
➢ Higher energy levels/states are called excited states.

➢ Ultraviolet and visible spectroscopy also known as electronic spectroscopy is used to measure the number of conjugation of
double bond and aromatic conjugation within the molecule.
➢ It involves the promotion of electrons from HOMO to LUMO (HOMO means Highest Occupied Molecular Orbital whereas
LUMO means Lowest Unoccupied Molecular Orbital).
➢ The HOMO-LUMO gap decrease as the conjugation increase.

➢ Since the energy levels of a molecule are quantized, the energy required to bring about the excitation is a fixed quantity.
➢ Thus, the electromagnetic radiation with only a particular value of frequency will be able to cause excitation.
➢ Clearly, if the substance is exposed to radiation of some different value of frequency, energy will not be absorbed and thus,
light or radiation will not suffer any loss in intensity.
➢ If radiation of a desired or correct frequency is passed or made to fall on the sample of the substance, energy will be
absorbed and electrons will be promoted to the higher energy states.
➢ Thus, light radiation on leaving the sample after absorption will be either less intense or its intensity may be completely lost.
➢ Substances absorbing in the visible range will appear colored to the human eye
➢ The ultraviolet region corresponds to 200-400 nm and visible region to 400-800 nm.
➢ UV-visible spectroscopy based on Beer-Lambert law.
A= log ( Io ⁄ I) = ϵ𝑐𝑙 or ϵ = 𝐴/𝑐𝑙
Where,
Io = Intensity of incident light, I = Intensity of transmitted light
ε = Molar absorptivity, l = Path length of sample
c = Concentration of sample, A = Absorbance
Transmittance (T) = I/Io
Absorbance (A): It is reciprocal of Transmittance
Absorbance (A) = -log(T) or log Io/I
Transmittance (T): The fraction of incident light transmitted is known as Transmittance.
Limitations of Beer Lambert Law : This law is not obeyed
i. When different forms of the absorbing molecules are in equilibrium as in keto-enol tautomers.
ii. When fluorescent compounds are present.
iii. When solute and solvent form complexes through some sort of association.
Measurement of Absorption Intensity
➢ The intensity of absorption is directly proportional to the transition probability.
➢ An allowed transition will have ε max value greater than 1000
➢ While those having low transition probability will have its value less than 1000 are not allowed or forbidden.
Selection Rules : The various electronic transitions which are governed by certain restrictions are called selection
rules. These are:
1. The transitions which involve a change in the spin quantum number of an electron during the transition do not
occur. When an electron undergoes a transition between different energy levels (for example, moving from one orbital to another), its
spin quantum number must remain unchanged.
Thus, singlet-triplet transitions are forbidden.
2. The transitions between orbitals of different symmetry do not occur.
For example, 𝑛 − 𝜋* transition is symmetry forbidden.

The wavelength of light corresponding to maximum

absorption is written as λmax.
It can be directly read from the horizontal axis as shown in
Figure.
The Figure shows the ultraviolet spectrum of vitamin A with
vertical line showing absorbance A which is equal to log
I0/I.
For vitamin A, the absorption maximum (λmax) is observed
at 324 nm.

Wavelength
Instrument
➢ A spectrophotometer is a device which detects the percentage transmittance of light radiation
➢ When light of certain intensity and frequency range is passed through the sample.
➢ The instrument compares the intensity of the transmitted light with that of the incident light.
The modern UV-Vis spectrometers
consist of light source,
monochromator, detector, amplifier
and the recording devices. .

➢ The most suitable sources of light are : Tungsten Filament lamp and hydrogen-
deuterium discharge lamp which cover the whole of the UV-visible region.
➢ Tungsten filament lamp is particularly rich in red radiations i.e., radiations with
wavelength 375 nm (Visible region), while the deuterium discharge lamp covers
the region below it (ultra-violet region).
➢ This spectroscopic technique is not useful below 200 nm (inaccessible region) since oxygen absorbs strongly at
200 nm and below.
➢ To study absorption below 200 nm, the whole path length is evacuated.
➢ The region below 200 nm is called vacuum ultra-violet region.
➢ The low wavelength region can be extended upto 150 nm by flushing the instrument with nitrogen which absorbs
below 150 nm.
➢ Most spectrophotometers are double beam instruments.
➢ The primary source of light is divided into two beams of equal intensity.
➢ Before dividing it into two beams, the incident radiation is dispersed with the help of a rotating prism.
➢ The various wavelengths of a light source are separated with a prism and then selected by slits such that the
rotation of the prism causes a series of continuously increasing wavelengths to pass through the slits for recording
purposes.
➢ The selected beam is monochromatic which is then divided into two beams of equal intensity. Dispersion grating
can also be employed to obtain monochromatic beam of light from polychromatic radiation (UV-VIS radiation).
➢ One of the beams of selected monochromatic light is passed through the sample solution and the other beam of
equal intensity is passed through the reference solvent.
➢ The solvent as well as the solution of the sample may be contained in cells made of a material which is
transparent throughout the region under study.
➢ Glass cannot be used since it absorbs strongly in the ultra-violet region.
➢ Silica cells can be used. These must be properly stored and their optical surfaces should never be handled.
➢ Quartz cells also serve the purpose best.
➢ Glass can be used satisfactorily in the visible region.
➢ This type of spectrometer is called double beam spectrophotometer.
➢ Each absorbance measurement on the solution is accompanied by a simultaneous measurement on the pure
solvent.
➢ Usually, samples are scanned in dilute solutions.
➢ One mg of the compound under investigation (Molecular weight 100-200) is accurately weighed and dissolved in a
suitable solvent to make the solution upto 100 ml volume.
➢ A little of this solution is taken in a silica cell.
➢ After the beams pass through the sample cell as well as the reference cell, the intensities of the respective
transmitted beams are then compared over the whole wavelength range of the instrument.
➢ The spectrometer electronically subtracts the absorption of the solvent in the reference beam from the absorption
of the solution.
➢ Hence, the effects due to the absorption of light by the solvent are minimized.
➢ In this way, the absorbance or the transmittance characteristic of the compound alone can be measured.
➢ The signal for the intensity of absorbance versus corresponding wavelength is automatically recorded on the graph.
Formation of Absorption Bands
➢ We expect the spectrum to consist of sharp peaks and each peak
will correspond to the promotion of electron from one electronic
level to another.
➢ But, actually sharp peaks are seldom observed and instead,
broad absorption bands are recorded.
➢ It is due to the fact that the excitation of electrons are also
accompanied by the constant vibratory and rotatory motion of the
molecules.
➢ The vibratory and rotatory modes are also quantized.

➢ A molecule in a particular electronic state is also quantized.

Clearly a molecule in a particular electronic state is also
accompanied by some vibrational and rotational states. The
differences between two adjacent electronic levels is more as
compared to the adjacent rotational levels while the difference
between the adjacent vibrational levels has some intermediate
value. The electronic excitation is superimposed upon rotational
and vibrational levels.

Electronic transitions
When molecule is getting excited by the absorption of electromagnetic radiation in UV-visible region then its
electrons are promoted from ground state to excited state or from bonding orbital to anti-bonding orbital.
 Types of electronic transitions
According to the molecular orbital theory, when a molecule is excited by the
absorption of energy (UV or visible light), its electrons are promoted from a
bonding to an antibonding orbital.
(i) The antibonding orbital which is associated with the excitation of 𝜎
electron is called 𝜎* antibonding orbital. So 𝜎 to 𝜎* transition takes place
when 𝜎 (sigma) electron is promoted to antibonding (𝜎) orbital. It is
represented as 𝜎 → 𝜎* transition.
(ii) When a non-bonding electron (n) gets promoted to an antibonding sigma
orbital (𝜎* ), then it represents n → 𝜎* transition.
(iii) Similarly 𝜋 → 𝜋* transition represents the promotion of 𝜋 electrons to an
antibonding 𝜋 orbital, i.e., 𝜋* orbital.
(iv) Similarly, when an n-electron (non-bonding) is promoted to antibonding
𝜋* orbital, it represents n→ 𝜋* transition.
The energy required for various transitions obey the following order : 𝜎 → 𝜎* > n → 𝜎* > 𝜋 → 𝜋* > n→ 𝜋*
1. 𝜎 → 𝜎* Transition
It is a high energy process since 𝜎 bonds are, in general, very strong.
The organic compounds in which all the valence shell electrons are involved in the formation of sigma bonds do not show
absorption in the normal ultra-violet region, i.e., 180–400 nm. For saturated hydrocarbons, like methane, propane etc.
absorption occurs near 150 nm (high energy).
Consider 𝜎 → 𝜎* transition in a saturated hydrocarbon.
Such a transition requires radiation of very short wavelength (High energy).
The usual spectroscopic technique cannot be used below 200 nm, since oxygen (present in air) begins to absorb strongly.
To study such high energy transitions (below 200 mμ), the entire path length must be evacuated. Thus, the region below
200 nm is commonly called vacuum ultraviolet region. This region is less informative.
 2. 𝑛 → 𝜎* Transition

➢ This type of transition takes place in saturated compounds containing one hetero atom with unshared pair of electrons
(n electrons).
➢ Some compounds undergoing this type of transitions are saturated halides, alcohols, ethers, aldehydes, ketones,
amines etc.
➢ Such transitions require comparatively less energy than that required for 𝜎 → 𝜎* transitions.
➢ Water absorbs at 167 nm, methyl alcohol at 174 nm and methyl chloride absorbs at 169 nm.
➢ In saturated alkyl halides, the energy required for such a transition decreases with the increase in the size of the
halogen atom (or decrease in the electronegativity of the atom).
3. 𝑛 → 𝜋* Transition

In this type of transition, an electron of unshared electron pair on hetero atom gets excited to 𝜋 * antibonding orbital. This
type of transition requires least amount of energy out of all the transitions discussed above and hence occurs at longer
wavelengths.
Example: Saturated aldehydes Show both the types of transitions, i.e., low energy 𝑛 → 𝜋* and high energy 𝜋 → 𝜋*
occurring around 290 nm and 180 nm respectively. Absorption occurring at lower wavelength is usually intense..

4. 𝜋 → 𝜋* Transition

➢ This type of transition generally shown in unsaturated molecules like alkenes, alkynes, aromatics, carbonyl compounds
etc.
➢ This transition required less energy as compare to 𝑛 → 𝜎* transition.
➢ Therefore, absorption occurs at longer wavelengths.
Absorption, intensity shift & UV spectrum
a. Bathochromic shift: It is also known as Red shift, in this case
absorption shift towards longer wavelength (𝜆max).
b. Hypsochromic shift: It is also known as Blue shift, in this case
absorption shift towards shorter wavelength (𝜆max).
c. Hyperchromic shift: Intensity of absorption maximum (𝜀max) increases.
d. Hypochromic shift: Intensity of absorption maximum (𝜀max) decrease.

Types of Absorption Bands

K Bands: K-bands originate due to 𝜋 → 𝜋* transition from a compound containing a conjugated system. Such type of
bands arise in compounds like dienes, polyenes, enones etc.
R band: Such type of bands originate due to 𝑛 → 𝜋* transition of a single chromophoric group and having at least one lone
pair of electrons on the hetero atom. R-bands are also called forbidden bands. These are less intense with 𝜀max value below
100.
B-band: Such type of bands arise due to 𝜋 → 𝜋* transition in aromatic or hetero-aromatic molecules. Benzene shows
absorption peaks between 230–270nm. When a chromophoric group is attached to the benzene ring, the B-bands are
observed at longer wave-lengths than the more intense K-bands.
E-bands. Such bands originate due to the electronic transitions in the benzenoid system of three ethylene bonds which are in
closed cyclic conjugation. These are further characterized as E1 and E2-bands. E1 and E2 bands of benzene appear at 184
and 204 nm respectively. E1 band which appears at lower wave-length is usually more intense than the E2-band for the
same compound which appears at longer wavelength.
Chromophores
➢ All those compounds which absorb light of wavelength between 400-800 nm appear colored to the human eye.
➢ Exact colour depends upon the wavelength of light absorbed by the compound.
➢ Originally, a chromophore was considered any system which is responsible for imparting colour to the compound.
➢ Nitro-compounds are generally yellow in colour.
➢ Clearly, nitro group is the chromophore which imparts yellow colour.
➢ Similarly, aryl conjugated azo group is a chromophore for providing colour to azo dyes.
➢ It is defined as any isolated covalently bonded group that shows a characteristic absorption in the ultraviolet or the
visible region.
There are two types of chromophores:
(a) Chromophores in which the group contains 𝜋 electrons and they undergo 𝑛 → 𝜋* transitions. Such chromophores are
ethylenes, acetylenes etc.
(b) Chromophores which contain both 𝜋 electrons and n (non-bonding) electrons. Such chromophores undergo two types of
transitions i.e., 𝑛 → 𝜋* < 𝜋 → 𝜋*. Examples of this type are carbonyls, nitriles, azo compounds, nitro compounds etc.
Auxochromes:
➢ An auxochrome can be defined as any group-which does not itself act as a chromophore but whose presence brings
about a shift of the absorption band towards the red end of the spectrum (longer wavelength).
➢ The absorption at longer wavelength is due to the combination of a chromophore and an auxochrome to give rise to
another chromophore.
➢ An auxochromic group is called colour enhancing group.
➢ Auxochromic groups do not show characteristic absorption above 200 mμ.
➢ Some common auxochromic groups are —OH, —OR, —NH2, —NHR, —NR2, —SH etc.
For example, benzene shows an absorption maximum at 255 nm whereas
aniline absorbs at 280 nm Hence, amino (—NH2) group is an auxochrome.
Factor affecting absorbance & intensity
a) Conjugation
Absorption shift towards longer wavelength, if double bonds (chromophore)
present in the molecule are in conjugation.
For example,
In compound ‘A’, double bonds are in conjugation therefore ‘A’ possessing
higher wavelength (𝜆max) as compare to compound ‘B’ (non-conjugated
derivative).
We know that, E = ℎ𝑐/𝜆
As the conjugation increase transition energy (E) between the orbitals decrease
and therefore wavelength (𝜆max) increase.
b) Effect of solvent
➢ A most suitable solvent is one which does not itself absorb in the region under investigation.
➢ A dilute solution of the sample is always prepared for the spectral analysis.
➢ Most commonly used solvent is 95% Ethanol.
➢ Ethanol is a best solvent as it is cheap and is transparent down to 210 nm.
➢ Commercial ethanol should not be used as it contains benzene which absorbs strongly in the ultraviolet region.
➢ Some other solvents which are transparent above 210 nm are n-hexane, methyl alcohol, cyclohexane, acetonitrile, diethyl ether
etc.
➢ The absorption maximum for the non-polar compounds is same in alcohol (polar) as well as in hexane (non-polar).
➢ The absorption maximum for the polar compounds is usually shifted with the change in polarity of the solvents.
Effect of Temperature
➢ It is known that the vibrational and the rotational states depend on temperature.
➢ As the temperature is decreased, vibrational and the rotational energy state of the molecules are also lowered.
➢ Thus, when the absorption of light occurs at a lower temperature, smaller distribution of excited states result.
➢ It produces finer structure in the absorption band than what is noticed at higher temperature.

Consider the UV spectrum of dodecapentaenoic acid in ether-alcohol solvent at 20 °C and –195 °C.
Woodward-Fieser rules (Calculation of 𝝀max (nm) in Explanation of terminology used in Woodward-
conjugated dienes) Fieser rules
Base value: 𝜆max (nm)
Parent value for Butadiene system 217
Heteroannular dienes 215
Homoannular dienes 253
Increments for
Double bond extending conjugation 30
R alkyl substituent or ring residue 5
Exocyclic double bond 5
Polar groupings
OCOCH3 0
OR 6
Cl, Br 5
NR2 60
SR 30
 Woodward-Fieser rules (Calculation of 𝝀max (nm) in α,β-unsaturated Carbonyl Compounds)
Base value: 𝜆max (nm)
Parent value for α,β-unsaturated Carbonyl 215 Increment in nm w.r.t. the carbonyl
system group
If X = alkyl group. 215 Chromophore α β γ δ or
For a compound, If X = H, 207 higher
= CH—COX,
if X = OH or OR 193 –OH 35 30 – 50
If the double bond and carbonyl group are 202 –OAc 6 6 6 6
with in the five membered ring –Cl 15 12 – –
Increments for
–Br 25 35 – –
Double bond extending conjugation 30
–OR 35 30 17 31
For a homoannular conjugated diene 39
–SR – 85 – –
For each double bond endocyclic in five or 5
seven membered ring except cyclo-pent-2- –NR2 – 95 – –
enone
Exocyclic double bond 5
For each alkyl α –position 10
substituent or ring
β –position 12
residue at the
γ and δ- position or 18
higher
➢ Infra-red spectrum is an important record which gives sufficient information about the structure of a compound.
➢ Unlike ultraviolet spectrum which comprises of relatively few peaks, this technique provides a spectrum containing
a large number of absorption bands from which a wealth of information can be derived about the structure of an
organic compound.
➢ The absorption of Infra-red radiations (quantized) causes the various bands in a molecule to stretch and bend with
respect to one another.
➢ The most important region for an organic chemist is 2.5 µ to 15 µ in which molecular vibrations can be detected
and measured in an infra-red spectrum and in a Raman spectrum.
➢ The ordinary infra-red region extends from 2.5 µ to 15 µ.
➢ The region from 0.8 µ to 2.5 µ is called Near infra-red and that from 15 µ to 200 µ is called Far IR Region.
➢ Mostly infra-red spectra of organic compounds are plotted as percentage transmittance against wave number.
➢ The relationship between wavelength and wave number is as follows:
 Instrumentation
➢ The most important source of Infra-red light for scanning the spectrum of an organic compound is Nernst glower which
consists of a rod of the sintered mixture of the oxides of Zirconium, Ytterium and Erbium.
➢ The rod is electrically heated to 1500 °C to produce Infra-red radiations.
➢ A rod of silicon carbide (Globar) can also be electrically heated to produce Infra-red radiations.
➢ To obtain monochromatic light, optical prisms or gratings can be used. For prism material, glass or quartz cannot be used since
they absorb strongly through most of the Infra-red region.
➢ Sodium chloride or certain alkali metal halides are commonly used as cell containers or for prism materials as these are
transparent to most of the Infra-red region under consideration.
➢ Light from the source is split into two beams.
➢ One of the beams is passed through the sample
under examination and is called the sample beam.
➢ The other beam is called the reference beam.
➢ When the beam passes through the sample, it
becomes less intense due to the absorption of
certain frequencies.
➢ Now, there will be a difference in the intensities of
the two beams.
➢ The two beams (Sample and Reference) are made to fall on a mirror M (chopper) with the help of two mirrors M1 and M2.
➢ The chopper (M) which rotates at a definite speed reflects the sample and the reference beams to a monochromator grating (B).
➢ As the grating rotates slowly, it sends individual frequencies to detector which converts Infra-red energy into electrical energy.
➢ It is then amplified with the help of amplifier (A).
❖ All the bonds in a molecule are not capable of absorbing infra-red energy but only those bonds which are
accompanied by a change in dipole moment will absorb in the infra-red region.
❖ The vibrational transitions which are accompanied by a change in the dipole-moment of the molecule are called
infra-red active transitions. Thus, these are responsible for absorption of energy in the Infra-red region.
❖ The vibrational transitions which are not accompanied by a change in dipole-moment of the molecule are not
directly observed and these are Infra-red inactive.
For example, vibrational transitions of C = O, N—H, O—H etc. bands are accompanied by a change in
dipole-moment and thus, absorb strongly in the Infra-red region.
But transitions in Carbon-Carbon bonds in symmetrical alkenes and alkynes are not accompanied by the
change in dipole-moment and hence do not absorb in the infra-red region.
❖ It is important to note that since the absorption in infra-red region is quantised, a molecule of the organic
compound will show a number of peaks in the infra-red region.
In the Infra-red spectroscopy (Region 2.5 μ – 15 μ), the absorbed energy brings about predominant changes in the
vibrational energy which depends upon:
1. Masses of the atoms present in a molecule,
2. Strength of the bonds, and
3. The arrangement of atoms within the molecule.

It has been found that no two compounds except the enantiomers can have similar Infrared spectra.
 Two kinds of fundamental vibrations are:
Stretching Bending
In this type of vibrations, the distance between the two In this type of vibrations, the positions of the atom
atoms increase or decrease but the atoms remain in changes with respect to the original bond axis.
the same axis

Stretching is of two types

1. Symmetric stretching: In this type, the movement of Bending is of four types
the atoms with respect to particular atom in a 1. Scissoring: In this type, two atoms approach each
molecule is in the same fashion. other.
2. Rocking: In this type, the movement of the atoms
takes place in same direction.
3. Wagging: Two atoms moves ‘up and down’ the
plane with respect to the central atom.
4. Twisting: in this type, one of the atoms moves up
2. Asymmetric stretching: In this type, the movement the plane while the other moves down the plane
of the atoms with respect to particular atom in a with respect to central atom
molecule is in the different fashion.
 Vibrational frequency
The value of the stretching frequency of a bond can be easily calculated by applying Hook’s law
Number of Fundamental Vibrations
➢ The Infra-red spectrum of a molecule results due to the transitions between two different vibrational energy
levels.
➢ The vibrational energy of a chemical bond is quantized and can have the value.
Polyatomic molecules may exhibit more than one fundamental vibrational absorption bands.
➢ The number of these fundamental bands is related to the degrees of freedom in a molecule.
➢ The number of degrees of freedom is equal to the sum of the co-ordinates necessary to locate all the atoms of a
molecule in space.
➢ Each atom has three degrees of freedom corresponding to the three cartesian co-ordinates (X, Y, Z) necessary to
describe its position relative to other atoms in a molecule.
3n degrees of freedom = Translational + Rotational + Vibrational
Where, n is the number of atoms in a molecule
➢ Rotational degrees of freedom result from the rotation of a molecule about an axis through the centre of gravity.
➢ Since we are concerned only with the number of fundamental vibrational modes of a molecule, so we calculate only
the number of vibrational degrees of freedom of a molecule.
➢ Since only three co-ordinates are necessary to locate a molecule in space, we say that a molecule has always
three translational degrees of freedom.
➢ In case of linear molecule, there are only two degrees of rotation.
➢ It is due to the fact that the rotation of such a molecule about its axis of linearity does not bring about any change in
the position of the atoms while rotation about the other two axes changes the position of the atoms.
for a linear molecule of n atoms.

In the case of non-linear molecule, there are three degrees of rotation as the rotation about all the three axes (X,
Y, Z) will result in a change in the position of the atoms.
So, for a non-linear molecule of n atoms, the vibrational degrees of freedom can be calculated as follows:
 Selection Rules (Active and Forbidden Vibrations)
Infra-red light is absorbed only when a change in dipole character of the molecule takes place.
i. If a molecule has a center of symmetry, then the vibrations are centrosymmetric and are inactive in the Infra-red but are active
in the Raman.
ii. The vibrations which are not centrosymmetric are active in Infra-red but inactive in Raman.

Factors Influencing Vibrational Frequencies In such cases, asymmetric vibrations always occur at higher wave
1. Coupled Vibrations and Fermi Resonance. We expect one number compared with the symmetric vibrations. These are called
stretching absorption frequency for an isolated C—H bond but coupled vibrations since these vibrations occur at different
in the case of methylene (—CH2 —) group, two absorptions frequencies than that required for an isolated C—H stretching.
occur which correspond to symmetric and asymmetric Similarly, coupled vibrations of —CH3 group take place at
vibrations as follows: different frequencies compared to —CH2— group. For methyl
group, symmetric vibrations are as follows:

➢ It may happen that the energy of an overtone level chances to

coincide with the fundamental mode of different vibration.
➢ This type of resonance is called Fermi Resonance. This can be explained by saying that a molecule transfers its energy from
fundamental to overtone and back again.
2. Electronic Effects.
➢ Changes in the absorption frequencies for a particular group take place when the substituents in the neighborhood of that
particular group are changed.
➢ The frequency shifts are due to the electronic effects which include Inductive effect, Mesomeric effects, Field effects etc.
➢ Under the influence of these effects, the force constant or the bond strength changes and its absorption frequency shifts from the
normal value.
(i) Formaldehyde (HCHO) 1750 cm–1
➢ The introduction of alkyl group causes + I effect which results
in the lengthening or the weakening of the bond and hence
(ii) Acetaldehyde (CH3CHO) 1745 cm–1
the force constant is lowered and wave number of absorption (iii) Acetone (CH3COCH3) 1715 cm–1
decreases.
➢ The introduction of an electronegative atom or group causes (i) Acetone (CH COCH ) 1715 cm–1
3 3
–I effect which results in the bond order to increase. Thus, the
(ii) Chloroacetone (ClCH2COCH3) 1725 cm–1
force constant increases and hence the wave number of
absorption rises. (iii) Dichloroacetone (ClCH2COCH2Cl) 1740 cm–1
3. Hydrogen bonding.
➢ Hydrogen bonding brings about remarkable downward
frequency shifts.
➢ Stronger the hydrogen bonding, greater is the absorption shift
towards lower wave number than the normal value.
➢ Generally, intermolecular hydrogen bonds give rise to broad
bands whereas bands arising from intramolecular hydrogen
bonds are sharp and well defined.
4. Effect of Bond Order
➢ Bond order affects the position of absorption bands.
➢ Higher the bond order larger is the band frequency.
➢ A C-C triple bond is stronger than a C=C bond, so a C-C triple bond has higher stretching frequency than does a C=C bond.
 Nuclear Magnetic Resonance Spectroscopy
➢ Nuclear Magnetic Resonance (NMR) is a spectroscopy technique which is based on the
absorption of electromagnetic radiation in the radio frequency region 4 to 900 MHz by nuclei
of the atoms.
➢ Proton Nuclear magnetic resonance spectroscopy is one of the most powerful tools for
elucidating the number of hydrogen or proton in the compound.
➢ Spectroscopy determines the physical and chemical properties of atoms or the molecules in
which they are contained and provide detailed information about the structure, dynamics,
reaction state, and chemical environment of molecules.

35
The nucleus of a hydrogen atom (proton) behaves as a spinning bar magnet because it possesses both electric and
magnetic spin.

NMR spectroscopy employs an magnetic energy absorption process, which orients spinning nuclei in a strong
external magnetic field.

1H

13C

15N

19F

31P

Magnetic: Nonmagnetic:
o All nuclei with odd number of protons o Nuclei with even number of both protons and neutron
o All nuclei with odd number of neutrons
 𝜷
P+ P+

P+
P+
𝜷 alignment opposes the applied magnetic field ∆𝐄
and is higher in energy than 𝜶alignment.

P+
P+

P+ P+
𝜶
𝐇𝟎
No applied magnetic field Influence of applied magnetic field

𝜔 = 𝛾𝐻0 2𝜋𝜇
𝛾=
2𝜋𝜈 = 𝛾𝐻0 ℎ𝐼
𝛾𝐻0 𝜇𝐻0
𝜈= ℎ𝜈 =
2𝜋 𝐼 37
 Number of Signals
➢ The number of signals in the nmr spectrum tell the number of different sets of equivalent protons in a
molecule.
➢ Each signal corresponds to a set of equivalent protons. It may be noted that magnetically equivalent
protons are chemically equivalent protons.

38
➢ Chemically equivalent protons must also be stereo-chemically equivalent
➢ A particular set of protons are said to be chemically equivalent only if they remain in exactly similar
environment when the stereo-chemical formula of the molecule under consideration is written

39
Instrumentation
NMR spectrophotometer makes use of
• a magnet,
• a radio-frequency,
• a detector and
• an amplifier.

Working
▪ The sample under investigation is taken in a glass tube which is placed between
the pole faces of a magnet.
▪ A radio-frequency source is made to fall on the sample.
▪ A signal is detected if the nuclei in the sample resonates with the source, i.e.,
energy required to flip the proton is the same as that of the source.
▪ Energy is transferred from the source via nuclei to the detector coil.
▪ The output from the detector is recorded after amplification.
40
▪ For practical purposes, radio-frequency source is held steady at the said frequency and field strength
is varied by placing small electromagnet to the pole faces of the main magnet.
▪ By increasing the current flowing through these electromagnets, the total field strength is increased.
▪ As the field strength increases, the precessional frequency of each proton increases until resonance
with the radio-frequency source takes place.
▪ As a proton (or a set of equivalent protons) comes to resonance, the signal from the detector
produces a peak on the chart paper.
▪ The nmr spectrum consists of series of peaks that correspond to different applied field strengths.
▪ Each peak means a set of protons.

42
 Positions of Signals (Chemical Shift)

▪ The positions of the signals in the spectrum help us to know the nature of protons viz., aromatic, aliphatic,
acetylenic, vinylic, adjacent to some electron attracting or electron releasing group etc.
▪ Each of these types of protons will have different electronic environments and thus, they absorb at different
applied field strengths.
▪ It is important to note that it is the electronic environment which tells where a proton shows absorption in the
spectrum.
▪ When a molecule is placed in a magnetic field, its electrons are caused to circulate and thus, they produce
secondary magnetic fields i.e., induced magnetic field.
▪ Rotation of electrons about the proton itself generates a field in such a way that at the proton, it opposes the
applied field.
▪ Thus, the field felt by the proton, is diminished and the proton is said to be shielded.
▪ If the induced field reinforces the applied field, the proton feels a higher field strength and thus, such a proton
is said to be deshielded.

43
 Chemical Shifts
▪ Such shifts (compared with a standard reference) in the positions of nmr absorptions which arise due to the
shielding or deshielding of protons by the electrons are called chemical shifts.
▪ For measuring chemical shifts of various protons in a molecule, the signal for tetramethyl silane (TMS) is taken
as a reference.
▪ Due to the low electronegativity of silicon, the shielding of equivalent protons in tetramethyl silane is greater
than most of the organic compounds.
▪ Therefore, nmr signal for tetramethyl silane is taken as a reference and chemical shifts for different kinds of
protons are measured relative to it.

44
• For chemical shift Delta (δ) or Tau (τ) scales are commonly used.
• In majority of organic compounds, protons resonate at a lower field than the protons of tetramethyl
silane (TMS).
• Thus assigning delta value for TMS equal to zero, a scale can be defined in which most proton
resonances are of the same sign.
• Any proton or set of protons which absorb at a field lower than TMS is given a positive value for δ,

45
• Tetramethyl silane is the most convenient reference and has the following characteristics:
1. It is chemically inert and miscible with a large range of solvents.
2. Its twelve protons are all magnetically equivalent.
3. It is highly volatile and can be easily removed to get back the sample.
4. It does not take part in intermolecular associations with the sample.
5. Its resonance position is far away from absorptions due to protons in most organic

where Δν is the frequency shift.

The value of δ is expressed in parts per million
(ppm).
Most chemical shifts have δ values between 0
and 10.

46
 Factors Influencing Chemical Shift
Inductive effect
➢ A proton is said to be deshielded if it is attached with an electronegative atom or group.
➢ Greater the electronegativity of the atom, greater is the deshielding caused to the proton.
➢ If the deshielding is more for a proton, then its δ value will also be more.

▪ Two signals are expected for each of the two compounds.

▪ Deshielding for protons ‘a’ in compound (i) is more than that for similar protons in compound (ii).
▪ As the distance from the electronegative atom increases, the deshielding effect due to it diminishes.
▪ Protons ‘b’ are comparatively less deshielded and hence will resonate at comparatively lower value of δ.

47
Van der Waal’s deshielding
The chemical shift also depends on the influence of bulky side groups

Clearly, electron cloud of a bulky group (hindering group) will tend to repel the
electron cloud surrounding the proton. Thus, such a proton will be deshielded and
will resonate at slightly higher value of δ than expected in the absence of this effect.
48
Anisotropic effects (Space effect)
➢ The deshielding effect on protons attached to C=C is higher than that can be
accounted for by the inductive effect alone.
➢ Aldehydic and aromatic protons are much more deshielded.
➢ Alkyne protons appear at relatively low value of δ.
➢ The values of δ (chemical shift) in each case can be justified by explaining the
manner in which the π electrons circulate under the influence of the applied field.
➢ Consider an alkene. It is so oriented that the plane of the double bond is at right
angles to the applied field.

➢ Induced circulation of π electrons generates

induced magnetic field which is diamagnetic around
carbon atom and paramagnetic in the region of the
alkene protons.
➢ Thus the protons will feel greater field strength and
hence resonance occurs at lower applied field.
49
➢ In case of benzene, loops of δ electrons are delocalized cylindrically over the
aromatic ring.
➢ These loops of electrons are induced to circulate in the presence of the applied
field producing ring current.
➢ The aromatic protons (around the periphery of the ring) experience a magnetic
field greater in magnitude than the applied field.

➢ Such protons are said to be

deshielded and hence,
smaller applied field (higher
value of δ will be required to
bring them to resonance.

50
Hydrogen bonding

➢ It has been found that a hydrogen atom exhibiting property of hydrogen bonding
in a compound absorbs at a low field in comparison to the one which does not.
➢ The hydrogen bonded proton being attached to a highly electronegative atom will
have smaller electron density around it.
➢ Being less shielded, the field felt by such a proton will be more and hence
resonance will occur downfield.
➢ The downfield shift depends upon the strength of hydrogen bonding.

51
Solvents Used
➢ A substance free of proton should be used as a solvent, i.e., which does not give
absorption of its own in NMR spectrum.
➢ Moreover, the solvent should be capable of dissolving at least 10% of the
substance under investigation.
Following solvents are commonly used in NMR spectroscopy:
(i) Carbon tetrachloride—CCl4
(ii) Carbon disulphide—CS2
(iii) Deuterochloroform—CDCl3
(iv) Hexachloroacetone—(CCl3)2CO etc.

52
Splitting of the Signals
➢ It is already pointed out that each signal in an nmr spectrum represents one kind or
one set of protons in a molecule.
➢ It is found that in certain molecules, a single peak (singlet) is not observed, but
instead, a multiplet (group of peaks) is observed.
a b
➢ For example: CH3CH2Br
➢ This molecule has two kinds of protons in it and thus, two signals are expected in
its nmr spectrum.

➢ It has been observed that for

each kind of protons, we do not
get singlets but a group of peaks
are observed.
➢ For ‘a’ kind of protons (CH3), a
triplet, i.e., a group of three
peaks is observed and a quartet
(group of four peaks) is noticed
for ‘b’ kind of protons (—CH2—). 53
Spin-spin coupling
Consider a molecule of ethyl bromide (CH3CH2 Br).
The spin of two protons (—CH2—) can couple with the adjacent methyl group (—
CH3) in three different ways relative to the external field. The three different ways of
alignment are:

Similarly, the spin of three protons (CH3—) can couple with the adjacent methylene
group (—CH2—) in four different ways relative to the external field.
The splitting of a signal is due
to the different environment
of the absorbing proton not
with respect to electrons but
with respect to the nearby
protons
54
There is a formula for predicating the number of peaks base on the neighboring
hydrogens and that is known as the n + 1 rule, where n is the number of neighboring
protons.

55
56
Some Important NMR Spectra

57