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Interactions of Radiation and Matter:

-It is for obtaining information about a sample.
-Sample is excited or stimulated by : Heat, Electrical,Light, Particles, Chemical reaction etc
-Prior to excitation the analyte is expected in the lowest energy state(Ground state).
-The radiation emitted & absorbed are measured as these contain information of analytes.



Stimulus(Excitation sources):

1.For Emission spectroscopy & Chemiluminescence
(e.g. flame & plasma emission spectroscopy, fluorescence spectroscopy etc)

Stimulus:
i)Bombardment with electrons or other elementary particles
(result: X-ray).

ii)By electric current/A.C. spark/D.C. arc/ furnace(heat)
(results: UV/Vis/IR radiations).
iii)By EM radiation(result: fluorescence).
iv)By exothermal chemical reaction
(result: chemiluminescence)

2.For Absorption spectroscopy & Photoluminescence
(e.g UV/Vis, IR, fluorescence & phosphorescence spectroscopy)

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Stimulus:
Electromagnetic radiation

Types of spectra:
1)Emission spectra 2)Absorption spectra

i)Emission spectra:
-EM radiation is produced when excited particles (atoms,ions or molecules) relaxes to lower energy levels
by giving up their excess energy as photons.

-The emitted radiation is passed through a prism or a grating & examined directly with a spectroscope.

-The spectrum thus obtained is Emission spectrum

-It is a plot of intensity of emitted radiation vs. WL or frequency.

Types of emission spectra:

i)Line emission spectra ii)Band emission spectra. iii)Continuous emission spectra.

i)Line spectra:
-A line spectra consists of discrete irregular spaced lines.
(produced in UV/Vis region)
-Substances in gaseous atomic state give this spectra.
-Width of a line is about 10
-5
nm.
-When the atom gets excited by electric or thermal method, its electrons move from inner orbitals to outer
orbitals(valence orbital to higher energy orbital).
-The atom returns to ground state after 10
-8
s, emitting a photons.
-The discrete spectral line because of the emitted radiation from the excited atoms is the basis of
emission spectroscopy.
-In order for any element to emit a single spectral line, energy equivalent to the excitation potential of the
element must be absorbed.

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ii)Band emission spectra.
- It is given by the gaseous excited molecules or radicals.
-Group of lines are so close together that under ordinary conditions they appear into a continuous band.
-In this, numerous quantised vibrational levels superimpose on the ground-state electronic energy level of
molecule.
-The band is also composed of various rotational energy levels as well.

-Relaxation from one electronic state to another electronic state is via slow collisional transfer of energy (Hence
relaxation by photon transfer is favoured)


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iii)Continuous spectra
-Incandescent solid like iron or carbon emits a continuous spectra.
-These spectra are devoid of sharp lines or discrete bands.
-Do not depend upon the chemical composition but rather on temperature of the emitting surface.
-The spectra obtained whenever matter in the bulk is heated until they glow.
-These spectra are avoided by volatilizing sample before the excitation.


2)Absorption spectra:
a)Line spectra(atomic absorption)
b)Band spectra(molecular absorption)
-Sample may be solid, liquid & gas.
-EM radiation is transferred to atoms , ions or molecules.
-Layers of sample selectively remove radiation of certain frequency.
-Energy difference between Gr.state & one of the excited state of substance is quantised & characteristic.
-The frequencies of the absorbed radiation is useful for the characterisation of the constituent of a sample
matter.
-An absorption spectrum is a result of plotting absorbance Vs. frequency/WL.
a)Line spectra(atomic absorption)
-Upon passing UV/Vis radiation through monoatomic particles, absorption is a result.
e.g, gaseous mercury or sodium
-Absorption occurs only in few well-defined frequencies.
-The simplicity is attributed to availability of small No. of possible energy states in the particles.

-In case of sodium, most intense absorption occur at 589.3 nm. followed by emission of yellow colour.
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b)Band spectra(molecular absorption)

E
int
= E
elect.
+ E
vib.
+ E
rot.

-The energy associated with the mentioned types are quantized. i.e.
Each energy components assumes only certain value for a given molecule.
-On irradiation with many wavelength, the molecules abstract from the incident beam those wavelengths
corresponding to photons of energy appropriate for the permitted molecular energy transitions.
-Radiation of other wavelengths are simply transmitted.
-The relative energy required for electronic, vibrational & rotational transitions are approximately 10000:100:1
respectively.
-Passage of molecules from higher to lower energy level is followed by the release of energy(emission)
-The region of the absorption is determined by the electronic energy levels of the molecule in absorption of
visible & UV radiation
Hence,
Increase of electronic energy level of a molecule is followed by absorption of visible & UV radiation.

-Vibrational & rotational transitions superimpose upon the electronic transition.

The resulting absorption involves a band of wavelengths rather than a single line(appears nearly continuous
spectra)

-The variation of the gain of energy approximates to a Gaussian distribution.
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