PH 802

ATOMIC AND MOLECULAR SPECTROSCOPY

LT P : ( 3 - 0 - 1 ) 4

BY

PROF. UDAYASHANKAR N K
DEPARTMENT OF PHYSICS
NITK SURATHKAL

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 PH802
Atomic and Molecular Spectroscopy

L1 Introduction to Spectroscopy
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Basic Concepts-1

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 Introduction to Atomic and Molecular Spectroscopy

The scope, objectives and definitions

Spectroscopy is the study of the radiation absorbed, emitted, reflected or scattered by a substance or it is the
study of interaction of EM waves and matter.

Applications :
Material characterization, Nature of chemical bonds, Qualitative and quantitative analyses, Chemical
composition of Interstellar space, etc.

Timeline (Historical Background)

1665 : Newton produced prism ‘spectrum’
1814 : Fruanhoffer observed dark lines in the solar spectrum
1859 : Kirchoff and Bunsen
1885 :Balmer formula
1906 : Lymann series
1926 : Wave Mechanics : Schrodinger wave equation
1960 : Lasers
2000 : Sophisticated Computers

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CHARACTERIZATION OF ELECTROMAGNETIC RADIATION -

Representing EMR : A simple harmonic wave propagating from a source and travelling in
straight lines except when reflected / refracted.

Any SHW has the property of sine wave, defined by

y= Asinϴ

where, y= displacement
ϴ= phase angle (0 to 2π )
A = Amplitude

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Here point P travels with uniform angular velocity  rad/s in a circular path of radius
A

ϴ = t radians.

In 1 second the pattern will repeat ‘/2π’ times and this is referred to as frequency ‘’.

So, y = A sin ϴ = A sin t= A sin 2π t (1)

and we can plot this displacement against time as shown in Fig. 1.2. 5
Now, we need the variation of displacement (y) with distance (x) for a travelling wave.
Let c be speed of wave.

So, x= ct ( distance= speed x time)

replacing this in equation (1) we get,
___(2)

But, c = λ
___(3)

Now, wave number = ῡ = 1/λ cm-1

y= A sin 2πῡx
and  = ῡc

units of wavelength
and conversions -
1 μm = 10-6 m
1 nm = 10-9 m
Fig. 1.3 The concept of a travelling wave with a wavelength 1 Å = 10 -10 m 6
 In spectroscopy, sometimes energy is expressed in cm-1

E = h

Substituting  = ῡc we get,
E = hῡc
If, ῡ = E /hc = 1 cm-1
Then,
E = hῡ c = ( 6.6 x 10-27ergs sec ) 1 cm-1 ( 3 x 1010 cms-1)
E= 1.986 x10-16 ergs/molecule

and, 4.186 x 10 7 ergs = 1 calorie

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i.e.,

Now,

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Kr(86)- Orange line,  = 6058 Å International standard of length (1960)
 = 6057.802106 Å, from spectroscopic measurements
1 m = 1,650,763.73 wavelengths of Kr(86) wavelengths (2p -5d5) 10

Summary

Properties which change during em interaction with matter –

frequency(),wave number (ῡ ), wavelength(), phase (), amplitude(), intensity(I), energy,  (1/cm)

and also polarisation.
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