Buffer-gas effect on the rotovibrational line intensity distribution: Analysis of possible mechanisms
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Line intensities Am (\(\)) of the HF fundamental band (T=293 K) are found to decrease linearly with the buffer-gas (Xe) density (\(\)-16 Amagat). The obtained slopes \(\) of the A m (d)/ A m (0) vs.\(\) plots are maximum at | m | =1 (\(\)) and rapidly drop with |m|. Many possible mechanisms are considered; the most effective one appears to be the HF-Xe bimer formation, with the equilibrium constant strongly depending on the rotational quantum number. The rigid-rotator approximation used gives the density derivatives considerably smaller than the measured ones. The disbalance may be lessened for vibrating rotators by allowance for the interband intensity transfer induced by the vibrational modulation of short-range forces.
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