On the determination of absolute intensities from single- and multiple-path absorption measurements

Abstract

The physical principles involved in conventional absolute intensity measurements are reviewed. Experimental difficulties rule out the use of extrapolation techniques for some spectral transitions. For this reason it is of interest to re-examine the possibility of using total absorption measurements, in conjunction with the curves of growth, for making intensity estimates. Extrapolation methods yield results which are independent of spectral line shape. Use of the curves of growth, on the other hand, implies the assumption that the line contour can be described by combined Doppler and Lorentz broadening. The curves of growth permit a unique correlation between total absorption and f-value either for spectral lines with pure Doppler broadening or for pure collision broadening. Furthermore, a simple experimental procedure can be devised for estimating both the absolute intensity and the spectral line profile on the basis of single-path and multiple-path absorption measurements. The suggested procedure involves absorption' measurements for optical densities (path lengths) under conditions in which the integrated fractional absorption is a relatively sensitive function of spectral line shape. Representative calculations referring to utilization of the proposed method have been carried out for spectral lines belonging to the ^2∑→^2II transitions, (0,0)-band, of OH, and also for lines belonging to the fundamental vibration-rotation spectrum of CO.