Wavelength modulation absorption spectrometry from optically pumped collision broadened atoms and molecules

A theoretical investigation of the influence of optical pumping on wavelength modulation absorption spectrometry (WMAS) signals from collision broadened atoms and molecules is presented. General expressions for the nf-WMAS signal from atomic and molecular systems, modeled as three-level systems that can accommodate both optical saturation and optical pumping, are derived by the use of a previously developed Fourier series-based formalism in combination with rate equations solved under steady-state conditions. The expressions are similar to those describing the nf-WMAS signal from two-level systems that can accommodate optical saturation [Schmidt FM, Foltynowicz A, Gustafsson J, Axner O, WMAS from optically saturated collision-broadened transitions. JQSRT 2005;94:225-54], the difference being the value of the saturation flux, wherefore the general parametric dependence of WMAS signals from optically pumped systems is the same as that from optically saturated systems. The additional effect of optical pumping on the WMAS signal is investigated for three typical cases: molecules or atoms in an ordinary atmosphere, atoms in an inert atmosphere, and atoms or molecules possessing metastable states. The possibility to describe any of these systems with a two-level model is investigated.