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Frequency‐dependent branching ratio in the infrared multiphoton photochemistry of diethyl carbonates
Author(s) -
Farneth William E.,
Thomsen Marcus W.,
Beck Thomas L.
Publication year - 1990
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610030903
Subject(s) - chemistry , diethyl carbonate , ethylene , fluence , ethylene carbonate , branching (polymer chemistry) , decomposition , irradiation , ethanol , photochemistry , rrkm theory , infrared , carbonate , analytical chemistry (journal) , organic chemistry , reaction rate constant , kinetics , optics , ion , physics , electrode , quantum mechanics , nuclear physics , electrolyte , catalysis
Unimolecular decomposition of 0·1 Torr of diethyl carbonate, diethyl‐ d 5 carbonate and diethyl‐ d 10 carbonate induced by irradiation with a CO 2 TEA laser was investigated. In all cases only ethylene, ethanol and CO 2 were obtained. In the case of diethyl‐ d 5 carbonate, both ethylene‐ d 4 and ethylene‐ d 0 were observed together with the corresponding isotopic variants of ethanol. The chemical branching ratio was determined as a function of irradiation frequency and laser fluence by analysis of the ethylene‐ d 0 /ethylene‐ d 4 ratio. RRKM theory applied to the branching ratio data requires very different average energies for two sets of fluence and frequency conditions that give identical total yields.