Spectroscopy techniques

Energy is Quantized
The energy of atoms and molecules is quantized.
They can only exist in allowed energy states or levels

Electronic energy levels

in a H atom

1s 2s 2p 3s 3p

The lowest energy state

has the single electron in
the 1s orbital

1s1 www.hemakumar.in
 Absorption and Emission of EMR
When EMR is absorbed or emitted by matter is
does so in whole photons only (NOT fractions)

Absorption involves E2
promotion from a E = h
lower energy state to
a higher one E1

Emission results in a E2
jump from a higher E = h
energy level to a
lower energy level E1
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 E2
E = h Intensity

E1

 Frequency

Intensity

E2
E = h
 Frequency
E1
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 1. Absorption Spectroscopy

Slit
Monochromator

Detector
Light Sample
Source

Slit

Recorder
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 Techniques of Wavelength Selection

1. Filters
• Absorption filters
– Coloured glass or
gelatin
– Normally broad
spectral bandwidth
• Cutoff or bandwidth
filters
– Can be combined to
provide narrower
bandwidth
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 Techniques of Wavelength Selection

2. Prism Monochromators

2

Prism 1 Slit
Entrance Collimating
slit lens Focussing
lens
Bunsen prism monochromator Focal
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plane
 Techniques of Wavelength Selection
3. Diffraction Grating Monochromators
– Glass or plastic plate covered with fine lines
– Reflect light of different wavelengths at different angles.
Condition for constructive interference (transmission) must
be achieved where the path difference between adjacent
beams must be an integral number of wavelengths
n = d(sin i + sin r) where n is the diffraction order

.
n=1 n=2

i r
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3. Diffraction Grating Monochromators
Concave mirrors

Reflection Grating
1 2

Entrance slit www.hemakumar.in Exit slit

3. Diffraction Grating Monochromators

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 EMR Detectors for Spectroscopy

1. Photographic Plates

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 EMR Detectors for Spectroscopy
2. Phototubes and Photomultipliers

Use the photoelectric effect to convert photons into

a measureable electric current

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 EMR Detectors for Spectroscopy
3. Silicon Photodiodes
Consist of a p-n silicon junction which increases
in conductivity when exposed to UV-visible
radiation. The change in conductivity is used
to measure the light intensity.

Photo Diode Array Detectors

A series of such photodiodes can be constructed
and used to simultaneously detect the radiation
of different wavelengths separated by a
monochromator www.hemakumar.in
 Origin of an Absorption Peak

Energy Transition E2
E = h

E1

Absorption Spectrum
Intensity

 Frequency
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Absorption Spectrum

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Absorption Spectrum

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 2. Emission Spectroscopy

Monochromator
Sample

Detector

Slit
Excitation
Energy

Heat
Electrical
EMR Recorder
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 Origin of an Emission Peak

Energy Transition E2
E = h
Excitation

E1

Emission Spectrum
Intensity

 Frequency
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 3. Fluorescence Spectroscopy
Monochromator
Sample

em Detector
ex
Slit
Slit

Monochromator

Slit Recorder

Light
Source
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 Origin of a Fluorescence Peak
E2
Radiationless energy loss
Energy Transition E3
E = hex E = hem

E1

Emission Spectrum
Intensity

em Frequency
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Forensic Application of Fluorescence
Visualization of fingerprints

Fingerprint visualized Cyanoacrylate Cyanoacrylate

by redwop fluorescent fumed + fumed
fingerprint powder Rhodamine 6G
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 4. Chemiluminescence
Excitation to a higher molecular electronic state by
a chemical reaction followed by emission of EMR

E2

Excitation by a E = h
chemical reaction

E1
Chemiluminescence Observed in Nature
e.g. firefly, fungi, jellyfish, bacteria, crustacea and fish
all may exhibit bioluminescence.

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