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 hat 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.
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