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Vibrational energy transfer from chemically activated 1,4‐cyclohexadiene
Author(s) -
Orchard S. Walter,
Ramsden Jennifer
Publication year - 1982
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550140106
Subject(s) - chemistry , isomerization , quenching (fluorescence) , benzene , photochemistry , excited state , thermal decomposition , decomposition , hydrogen , rrkm theory , activation energy , hexane , computational chemistry , reaction rate constant , kinetics , organic chemistry , atomic physics , catalysis , fluorescence , physics , quantum mechanics
The thermal isomerization of cis , anti , cis ‐tricyclo[3.1.0.0 2,4 ] 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, SF 6 , CO 2 , N 2 , 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 〈Δ E 〉 deduced (at 528 K and in units of kJ/mol) were: parent compound and SF 6 , 7; CO 2 , 5; N 2 , 4; He, 2. The study confirmed the utility of this unimolecular chemical activation system for energy transfer studies.