Photon Multiplier tube (PMT)

For observing the emission spectrum of the sample. consists of a photoelectric plate on which photons (from the fluorescence in the tube caused by spontaneous emission) strike causing it to emit electrons. It further consists of a series of dynodes which cause secondary emission thereby amplifying the current which can be fed to a CRO

Doppler broadening is observed because of frequency shift of the radiation (that is emitted or absorbed) due to the random thermal motion of the atoms

vz a 0 (1 ) c
Where 0 is corresponds to the transition frequency & vz is the velocity of the atom

Using the previous result and Maxwellian velocity distribution, the FWHM (Full Width at Half Maximum) of the Doppler broadened spectrum line can be derived which is

And in frequency units

For a 2s 1p transition in the H atom the Doppler broadening turns out to be around 55 GHz, while the hyperfine structure for ground state =1.42 GHz. Thus we cannot resolve the hyperfine splitting with conventional spectroscopy

To overcome this we can have the atom excited with two photons targeted at it from opposite directions. The Doppler shift caused by one would be negated by the other.

But now, the atom absorbs two photons. What is the transition that occurs? The calculations are rather involved but heres the gist. Its two stage: First, the electron makes a transition to a virtual state |k> which is a linear superposition of the states that is allowed by the selection rules from the initial state |i>. & the final stage again is one that is allowed from each of the states in the superposition |k>.

The experimental setup for two photon spectroscopy..

When the electron de-excites back there would be two wavelengths (its two stage again) We use a filter in front of the PMT to detect only one of the two frequencies

Above - The theoretical spectrum for Molecular Iodine & Below The experimental result for Doppler free spectroscopy with Hyperfine structure resolved

For further reading, consult: Wolfgang Demtrder, Laser Spectroscopy Basic Concepts and Instrumentation, Third edition, Springer Arthur L. Schawlow, Spectroscopy in a New Light Nobel Lecture, 8 December, 1981