You are on page 1of 10

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
ΔE=E e -E g

ROTATIONAL ENERGY (E rot ) . the molecule is said to possesses vibrational energy. 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.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.

With the help of molecular spectroscopy we can determine the electronic energy blevel. . • Sample is not chemically affected hence sample recovery possible. • It can also be used to monitor changing the concentrations of reactant or products in kinetic studies. 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. • It is also the basis of our understanding of color in the world around us. • The spectroscopic results are reliable. bond angles and strength of bonds.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. reproducible and correct. ADVANTAGES • Spectroscopy methods requires less time and less amount of sample (1 mg). • Emission spectroscopy is used for the study of energetically excited reaction product. bond length. TRANSLATIONAL ENERGY (E tr ) Energy of the molecule when during the motion centre of gravity of molecule changes.

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 .

Once a molecule undergoes the electronic transition. This vibrational structure of an electronic transition shows that the absorption spectrum consists of many lines instead of a single sharp electronic absorption line. The nucleus in a molecule has Coulombic forces acting on it from the electrons and other nuclei of the system. such as ionization. APPLICATIONS UV-VIS spectrometry can be used to detect one or more components in a solution and measure the concentration of these species. it may also used for obtaining structural information of substances. 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. In addition.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. particularly the organic compounds and it may as well help in establishing the identity of a . the theory states that it must undergo a vibration. This change brings it from the ground state to an excited state and results in the nuclei changing its vibrational state. the nuclear configuration of the molecule experiences no significant change. the resulting Coulombic forces serve to change the energy of the molecule. When the nucleus realigns itself with with the new electronic configuration.

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. In addition. ELECTRONIC TRANSITION IN UV-VISIBLE SPECTROSCOPY The absorption of UV or visible radiation corresponds to the excitation of outer electrons. The most important qualitative application of UV-VIS spectrometry is to detect the presence of unsaturation in the molecule. σ. σ. There are three types of electronic transition which can be considered. due to its versatility. 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.molecule. which can be considered as being packed on top of each electronic level. identifying or forming an absorbing species. The spectrum of a . the atoms can rotate and vibrate with respect to each other. inorganic and biochemical species accurately at fairly low concentrations of the order of 10‒4 to 10‒5 M or even lower. On the other hand. In a molecule. 1. Transitions involving d and f electrons (not covered in this Unit) When an atom or molecule absorbs energy. These vibrations and rotations also have discrete energy levels. accuracy and sensitivity UV-VIS spectrometry can be used for direct determination of a large number of organic. Absorbing species containing π. controlling factors that influence absorbance and validation of Beer and Lambert’s law. selection of the measurement wavelength. Transitions involving π. The quantitative determinations follow a general methodology involving four steps as. electrons are promoted from their ground state to an excited state. Transitions involving charge-transfer electrons 3. and n electrons 2.

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

000 L mol-1 cm-1 . Charge . Often (but not always).Transfer Absorption Many inorganic species show charge-transfer absorption and are called charge-transfer complexes.000 L mol-1 cm-1).e. π → π* transitions normally give molar absorbtivities between 1000 and 10. . This is caused by attractive polarisation forces between the solvent and the absorber. and so the energy difference between the excited and unexcited states is slightly reduced .resulting in a small red shift. This effect is greater for the excited state. This arises from increased solvation of the lone pair. Peaks resulting from n→ π* transitions are shifted to shorter wavelengths (blue shift) with increasing solvent polarity. This effect also influences n→ π* transitions but is overshadowed by the blue shift resulting from solvation of lone pairs. which lower the energy levels of both the excited and unexcited states. red shift) is seen for π → π* transitions. and range from 10 to100 L mol-1 cm1 . Molar absorbtivities from charge-transfer absorption are large (greater that 10. which lowers the energy of the n orbital. The solvent in which the absorbing species is dissolved also has an effect on the spectrum of the species. one of its components must have electron donating properties and another component must be able to accept electrons.Molar absorbtivities from n→ π* transitions are relatively low. For a complex to demonstrate charge-transfer behaviour. Absorption of radiation then involves the transfer of an electron from the donor to an orbital associated with the acceptor. the reverse (i.

SOLVENT EFFECT .

Causes of nonlinearity include: • • • • • • • Deviations in absorptivity coefficients at high concentrations (>0.e.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.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.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. absorbance (A) ∝ concentration (C)×path length (L) or A= ε C L Where ε 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. deviations can be minimized by using a relatively flat part of the absorption spectrum such as the maximum of an absorption band Stray light .