Vibrational energy transfer from chemically activated 1,4-cyclohexadiene

✍ Scribed by S. Walter Orchard; Jennifer Ramsden

• Publisher: John Wiley and Sons
• Year: 1982
• Tongue: English
• Weight: 571 KB
• Volume: 14
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550140106

✦ Synopsis

The thermal isomerization of cis, anti, ~is-tricyclo[3.1.0.0~~~] hexane was used to produce highly vibrationally excited 1,4-cyclohexadiene. The competition between unimolecular decomposition of the energized diene (to benzene and hydrogen) and collisional stabilization was studied using the parent compound, SF6, COz, Nz, and He as quenching gases. Quenching efficiencies decreased in the order given above. By applying RRKM theory to the isomerization and decomposition reactions, it was possible to calculate the step size in a stepladder model of the deactivation of cyclohexadiene. The step sizes (AE) deduced (at 528 K and in units of kJ/mol) were: parent compound and SF6,7; COz, 5; Nz, 4; He, 2. The study confirmed the utility of this unimolecular chemical activation system for energy transfer studies.