Vibrational Relaxation of Laser-Excited CO2-Polyatomic Mixtures

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Abstract
Laser‐excited vibrational fluorescence measurements have given rates for vibrational energy transfer from the asymmetric stretch of CO2 to several polyatomic molecules. Rate constants for energy transfer to the nearly resonant CD stretching vibrations in the deuterated species CD4, CD2H2, CD3Cl, CD3I, C2D2, CD2CH2, and C2D4 are compared to the corresponding normal hydrogen isotopes, and to the alkanes C2H6, C3H8, C5H12, and C6H14. The deuterated molecules are between 2 and 90 times more effective than the hydrogen isotopes at vibrationally deactivating CO2. Cross sections for energy transfer from CO2 to (CN)2, HCN, CH3CN, H2Se, CS2, and OCS are given, and rates for intermolecular and intramolecular energy transfer in several of the collision partners are deduced.