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Lecture 3 - Line Shapes

The document discusses line shapes in spectroscopy, distinguishing between homogeneous and inhomogeneous line shapes, with examples such as Lorentzian and Gaussian functions. It also covers the effects of pressure and Doppler broadening on spectral lines, and provides calculations for determining detectable concentrations of Mercury atoms based on absorption cross sections. Additionally, it references Heisenberg's uncertainty principle in relation to line broadening.

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185 views11 pages

Lecture 3 - Line Shapes

The document discusses line shapes in spectroscopy, distinguishing between homogeneous and inhomogeneous line shapes, with examples such as Lorentzian and Gaussian functions. It also covers the effects of pressure and Doppler broadening on spectral lines, and provides calculations for determining detectable concentrations of Mercury atoms based on absorption cross sections. Additionally, it references Heisenberg's uncertainty principle in relation to line broadening.

Uploaded by

ehfhehfbehhdhfhd
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Line shapes

Sept 4 2008
CHEM 5161
What determines the line width ?
Line shapes:
Homogeneous vs inhomogeneous
• Homogeneous line shape:
– All molecules behave in the same way
– Lorentz line shape
– Examples are: b=10 MHz/Torr
• Pressure broadening
• Natural lifetime broadening
• Transit time broadening

Heissenberg’s uncertainty principle:


Line shapes (cont):
H
Homogeneous vs iinhomogeneous
h
• Inhomogeneous
I h line
li shape:
h
– All molecules behave differently (distribution)
– Gaussian line shape
– Examples are:
• Doppler broadening
• Power broadening
Line shapes:
Homogeneous vs inhomogeneous
• Homogeneous line shape:
– All molecules behave in the same way
– Lorentz line shape
– Examples are:
• Natural lifetime broadening
• (Transit time broadening)
• (Power broadening)

Heissenberg’s uncertainty principle:


Lorentzian line shape function
Gaussian lineshape function

g(ν-ν0) = A exp –[(ν-ν0)2 / (2 α2)]


Voigt lineshape function

http://scienceworld.wolfram.com/physics/topics/SpectralLineshapes.html
• At what ppressure will the Doppler
pp
broadening (FWHM) equal the pressure
broadening (FWHM) for a room
temperature (20C) sample l off CO gas ffor a
pure rotational transition at 115 GHz, a
vibrational rotational transition at 2140 cm-
vibrational-rotational
1, and an electronic transition at 1537 Ǻ ?

Use a “typical”
typical pressure
pressure-broadening
broadening
coefficient of 10 MHz/Torr in all three
cases.
Example CO
115 GHz 2140cm-1 1537 A

• Doppler 10-8 Hz 5 10-3 cm-1 0.15 cm-1


• Pressure 15 Torr 450 Torr

– M = 28 amu
– T = 20 C
– b = 10 MHz Torr-11 = 3.33 10-44 cm-11 Torr-11
• The absorption cross section of Mercury
atoms is 3
3.3
3 10-14
14 cm2 (measured at

253.65nm with a spectral resolution of


0 015nm) Your instrument is capable of
0.015nm).
detecting an optical density of 10-4, and
measures over a pathlength of 1 m m. What
Hg concentration is detectable ?
• A:
A 105 < x < 106 molec
l m-33
• B: 106 < x < 107 molec m-3
• C: 107 < x < 108 molec m-3
• D: 108 < x < 109 molec m-3
• E: > 1010 molec m-3

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