Effects of field broadening and pump line selection on multi-level absorption in molecular systems

The problem of multi-level absorption of i.r. laser radiation in polyatomic gases is examined using the density matrix formalism. The general condition under consideration is that field broadening effects are significant, but the detailed and discrete features of the absorption spectra remain very important. Collisional effects are taken into account through macroscopic relaxation terms, but the cumulative effects of collisional relaxation are assumed to cause only minor perturbations to the overall vibrational-rotational populations over the optical pumping time scale of interest. Various approximate formulae are then derived for locating the optimum frequency for optical pumping of three consecutive anharmonic vibrational levels within a given normal mode and for predicting the intensity- and frequency-dependence of the resultant uppermost level population density during a quasi-steady state balance among the absorption, stimulated emission, dephasing collision and rotational relaxation rates. Numerical examples are illustrated for pumping of the three lowest vibrational levels within the non-degenerate asymmetric stretching mode of the linear triatomic molecule CO₂ for which the absorption spectra are relatively simple and well known. Some possible applications of these results to the problem of i.r. laser frequency conversion and to the interpretation of wavelength-selective i.r. photodissociation recently observed in many symmetric top molecules, such as BCl₃, SiF₄ and SF₆ for which the absorption spectra are much more complex and the spectroscopic constants much less certain, are also discussed.