Near-Resonant Vibrational Interactions of CO and CO2 with NO, PF5, SF6, and BCl3

摘要

The transfer of substantial amounts of vibrational energy from CO and CO2 to specific complex molecules has been observed in flow tube experiments by monitoring of the emission from the 4.6-micrometers fundamental band and the 2.3-micrometers first-overtone band of CO and from the 4.3-micrometers fundamental band and the 2.7-micrometers mixed-mode Fermi-resonance bands of CO2. Small amounts of BCl3, PF5, and NO were found to significantly reduce both the 4.7- and the 2.3-micrometers emission from CO. Similar effects were observed for the 4.3- and 2.7-micrometers emission of CO2 with the addition of PF5, SF6, and BCl3. These phenomena are caused in CO by near-resonant vibrational energy transfer between the vibrational levels of this molecule with the alternate levels of the degenerate vibrational modes of BCl3 and PF5, and the vibrational states of NO, and in CO2 by a similar process. (Author)