Role of initial rotation on vibrationally inelastic collisions: Enhancement and specificity in level to level rate constants for Li*2

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Abstract
Rate constants were measured by laser induced fluorescence for vibrational‐rotation changing collisions of Li*2(A 1Σ+) with Xe from initial vibration level vi=4 and initial rotation levels ji=14, 28, 44 with Δv=±1, ±2 and resolved final rotation levels jf. The jf distribution of kvi,ji→vf,jf peaks dramatically at high ji: for Δv=−1 the width (FWHM) is ≂28 for ji=14 and ≂5 for ji=44. The peak rate corresponds to a level to level cross section σ(vi=4, ji=44→vf=3, jf=48)=3 Å 2. Increasing ji from 14 to 44 also increases the total rate kjivi→vf =Σkjfviji→vfjf of vibrationally inelastic collisions by a factor of about 3. The magnitude of the mean total cross sections σjivi→vf is large, ranging from 1 Å2 (Δv=+2, ji=14) to 15 Å2 (Δv=−1, ji=44).

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