SPECTROSCOPY

Is the analysis of the electromagnetic radiation scattered or emitted by molecules. It deals with the
transition that a molecule undergoes between its energy levels upon absorption of suitable radiations
determined by quantum mechanical selection rules
Or
Spectroscopy is the study of the interaction of electro-magnetic radiation with matter. When matter is
energized (excited) by the application of thermal, electrical, nuclear or radiant energy, electromagnetic
radiation is often emitted as the matter relaxes back to its original (ground) state. The spectrum of
radiation emitted by a substance that has absorbed energy is called an emission spectrum and the
science is appropriately called emission spectroscopy.
ORIGIN OF SPECTRUM
Consider two energy levels of an atom/molecule. The one with lower energy is called ground state
energy level (E g ) and the one with higher energy is called exited state energy level (E e )
ABSORPTION SPECTRUM
Absorption spectrum arises when an electron in an atom or a molecule undergoes a transition from
lower energy level to the higher energy level with the absorption of a photon of energy hv.in this case
E=E e -E g

EMISSION SPECTRUM
Emission spectrum result when an electron in an atom or a molecule falls from the exited state to the
ground state with the emission of a photon of energy hv

Spectra can be broadly classified into two categories

ATOMIC SPECTRA
Arises from the transition of an electron between the atomic energy levels. In this only electronic
transition are involved
MOLECULAR SPECTRA
Arises from the transition of an electron between molecular energy levels. In this the energy of molecule
can change not only as a result of electronic transition but also due to transition between its rotational
and vibrational sates

MOLECULAR SPECTROSCOPY
ELECTRONIC ENERGY (E el )
Which is associated with the transition of an electron from the ground state energy level to the exited
state by the absorption of photons of suitable frequency
VIBRATIONAL ENERGY (E vib )
When the centre of gravity does not change during the to-and-fro motion of the nuclei of the molecule,
the molecule is said to possesses vibrational energy.
ROTATIONAL ENERGY (E rot )

The rotational energy of a molecule is the energy of molecule due to the rotation of molecule about the
axis perpendicular to the internuclear axis of molecule.
TRANSLATIONAL ENERGY (E tr )
Energy of the molecule when during the motion centre of gravity of molecule changes.
TOTAL ENERGY ACCORDING TO THE BORN-OPPENHEIMER APPROXIMATION
E=E el +E vib +E rot +E tr
E el >>E vib >>E rot >E tr
If E tr is negligible
Then
E=E el +E vib +E rot
APPLICATION OF MOLECULAR SPECTROSCOPY

It is used in structural investigation. With the help of molecular spectroscopy we can determine
the electronic energy blevel, bond length, bond angles and strength of bonds.

It can also be used to monitor changing the concentrations of reactant or products in kinetic
studies.

It is also the basis of our understanding of color in the world around us.

Emission spectroscopy is used for the study of energetically excited reaction product.

ADVANTAGES

Spectroscopy methods requires less time and less amount of sample (1 mg).

The spectroscopic results are reliable, reproducible and correct.

Sample is not chemically affected hence sample recovery possible.

ELECTRONIC/UV-VISIBLE SPECTROSCOPY

Visible range 12500-25000 Cm-1

UV range 25000-72000 Cm-1
It involve the transition of electrons within a molecule or ion from a lower to higher electronic energy
level or vice versa by the absorption or emission of radiation falling in the UV-visible range of
electromagnetic spectrum

FRANCK-CONDON PRINCIPLE
The Franck-Condon Principle describes the intensities of vibronic transitions, or the absorption or
emission of a photon. It states that when a molecule is undergoing an electronic transition, such as
ionization, the nuclear configuration of the molecule experiences no significant change. This is due
in fact that nuclei are much more massive than electrons and the electronic transition takes place
faster than the nuclei can respond. When the nucleus realigns itself with with the new electronic
configuration, the theory states that it must undergo a vibration.
The nucleus in a molecule has Coulombic forces acting on it from the electrons and other nuclei of
the system. Once a molecule undergoes the electronic transition, the resulting Coulombic forces
serve to change the energy of the molecule. This change brings it from the ground state to an
excited state and results in the nuclei changing its vibrational state. This vibrational structure of an
electronic transition shows that the absorption spectrum consists of many lines instead of a single
sharp electronic absorption line.
APPLICATIONS
UV-VIS spectrometry can be used to detect one or more components in a solution and measure the
concentration of these species. In addition, it may also used for obtaining structural information of
substances; particularly the organic compounds and it may as well help in establishing the identity of a

molecule. The most important qualitative application of UV-VIS spectrometry is to detect the presence
of unsaturation in the molecule. In addition, the changes in spectra due to the changes in the pH of the
solution or the solvent can provide useful information about the nature of the analyte. On the other
hand, due to its versatility, accuracy and sensitivity UV-VIS spectrometry can be used for direct
determination of a large number of organic, inorganic and biochemical species accurately at fairly low
concentrations of the order of 104 to 105 M or even lower. The quantitative determinations follow a
general methodology involving four steps as, identifying or forming an absorbing species, selection of
the measurement wavelength, controlling factors that influence absorbance and validation of Beer and
Lamberts law.
ELECTRONIC TRANSITION IN UV-VISIBLE SPECTROSCOPY
The absorption of UV or visible radiation corresponds to the excitation of outer electrons. There are
three types of electronic transition which can be considered;
1. Transitions involving , , and n electrons
2. Transitions involving charge-transfer electrons
3. Transitions involving d and f electrons (not covered in this Unit)
When an atom or molecule absorbs energy, electrons are promoted from their ground state to an
excited state. In a molecule, the atoms can rotate and vibrate with respect to each other. These
vibrations and rotations also have discrete energy levels, which can be considered as being packed on
top of each electronic level.

Absorbing species containing , , and n electrons

Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional
groups (chromophores) that contain valence electrons of low excitation energy. The spectrum of a

molecule containing these chromophores is complex. This is because the superposition of rotational and
vibrational transitions on the electronic transitions gives a combination of overlapping lines. This
appears as a continuous absorption band.
Possible electronic transitions of , , and n electrons are;

* Transitions
An electron in a bonding orbital is excited to the corresponding antibonding orbital. The energy
required is large. For example, methane (which has only C-H bonds, and can only
undergo * transitions) shows an absorbance maximum at 125 nm. Absorption maxima due
to * transitions are not seen in typical UV-Vis. spectra (200 - 700 nm)
n * Transitions
Saturated compounds containing atoms with lone pairs (non-bonding electrons) are capable
of n * transitions. These transitions usually need less energy than * transitions. They can be
initiated by light whose wavelength is in the range 150 - 250 nm. The number of organic functional
groups with n * peaks in the UV region is small.
n * and * Transitions
Most absorption spectroscopy of organic compounds is based on transitions of n or electrons to
the * excited state. This is because the absorption peaks for these transitions fall in an experimentally
convenient region of the spectrum (200 - 700 nm). These transitions need an unsaturated group in the
molecule to provide the electrons.

Molar absorbtivities from n * transitions are relatively low, and range from 10 to100 L mol-1 cm1
. * transitions normally give molar absorbtivities between 1000 and 10,000 L mol-1 cm-1 .
The solvent in which the absorbing species is dissolved also has an effect on the spectrum of the species.
Peaks resulting from n * transitions are shifted to shorter wavelengths (blue shift) with increasing
solvent polarity. This arises from increased solvation of the lone pair, which lowers the energy of
the n orbital. Often (but not always), the reverse (i.e. red shift) is seen for * transitions. This is
caused by attractive polarisation forces between the solvent and the absorber, which lower the energy
levels of both the excited and unexcited states. This effect is greater for the excited state, and so the
energy difference between the excited and unexcited states is slightly reduced - resulting in a small red
shift. This effect also influences n * transitions but is overshadowed by the blue shift resulting from
solvation of lone pairs.

Charge - Transfer Absorption

Many inorganic species show charge-transfer absorption and are called charge-transfer complexes. For a
complex to demonstrate charge-transfer behaviour, one of its components must have electron donating
properties and another component must be able to accept electrons. Absorption of radiation then involves
the transfer of an electron from the donor to an orbital associated with the acceptor.
Molar absorbtivities from charge-transfer absorption are large (greater that 10,000 L mol-1 cm-1).

SOLVENT EFFECT

BEER'S-LAMBERT LAW
It states that for a parallel beam of monochromatic radiation passing through a homogeneous solution
the absorbance is proportional to the product of the concentration and path length
i.e. absorbance (A) concentration (C)path length (L)
or A= C L
Where is the absorptive or molar extension coefficient of solution
Let I 0 and I are the intensity of incident and transmitted light respectively
Then transmittance, T=I/I 0
%T=I/I 0 100
And the logarithm of the reciprocal of the transmittance is termed as absorbance (A)
i.e. A=log(1/T)

where T=I/I 0

LIMITATION OF BEER'S-LAMBERT LAW

The linearity of the Beer-Lambert law is limited by chemical and instrumental factors. Causes of
nonlinearity include:

Deviations in absorptivity coefficients at high concentrations (>0.01M) due to electrostatic

interactions between molecules in close proximity
Scattering of light due to particulates in the sample
fluorescence or phosphorescence of the sample
Changes in refractive index at high analyte concentration
Shifts in chemical equilibrium as a function of concentration
Non-monochromatic radiation, deviations can be minimized by using a relatively flat part of the
absorption spectrum such as the maximum of an absorption band
Stray light