Abstract
High-resolution (0.002 cm −1) stimulated Raman spectroscopy has been applied to the study of both normal and satellite Q branches of the fundamental vibrational band of molecular oxygen. Using a pulsed molecular free-expansion jet to adiabatically cool the oxygen sample, satellite Q branches at 1554 and 1558 cm −1 that arise due to the splitting of the 3Σ g ground state by spin-spin and spin-rotation interactions were completely resolved for the first time. Measured intensity ratios for the ΔN ΔJ(J, N) = Q0(2, 1) and Q R(1, 1) lines, and for the Q S(0, 1) and Q P(2, 1) lines compare favorably with that for a coupling case intermediate between Hund's cases (a) and (b). Depolarization ratios, measured for a series of QQ -branch (unresolved) triplets, give a value 0.164 ± 0.004 for the depolarization ratio of the fundamental vibrational band.
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