Homogeneous line broadening absorption spectroscopy

Equation (7.22) is at the heart of spectroscopy. The positions of the absorption lines reflect the energy levels of the excited complex and the widths provide information about the lifetime and therefore about the coupling to the continuum states. The latter requires, however, that the measured widths are the true homogeneous line widths, i.e., unadulterated by poor resolution and/or thermal broadening, for example. Each resonance has a characteristic width. In Chapters 9 and 10 we will discuss how the final fragment distributions reflect the initial state in the complex and details of the fragmentation mechanism. 

However, when the frequency is coincident with the center frequency of the Doppler profile, the weak probe wave interacts with molecules whose absorption has already been reduced by the strong counterrunning wave. Consequently, the absorption of the probe wave has a resonant minimum equal in width to the homogeneous width and centered exactly on the Doppler-broadened absorption line. This method has been demonstrated in experiments using a CO2 laser operating at 10/um and SFe molecules (Basov et al. 1969), and now it is universally accepted in laser saturation spectroscopy. 

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