, 962 (1983).Nous avons CtudiC la photolyse du methyl-3-butkne-l (M3B1) et du mCthyl-2-butkne-l (M2B1) i 185 nm cn phase gazeuse. Les processus primaires de fragmentation observes confirment la prCpondCrance de la fragmentation via la rupture de la liaison P(C-C) avec formation concomitante de radicaux mCthyles et soit de radicaux a-mCthallyles (cas du M3B1) soit de radicaux P-mCthallyles (cas du M2B1). La comparaison de ces deux systttmes inspire une mCthode trks primitive quant B la determination de I'Cnergie supportCe par les radicaux mCthallyles: 48% des radicaux C4H7* ainsi produits ont une Cnergie interne entre 42 et 58 kcal mol-' a 185 nm. D'autres comparaisons sont faites avec ce qui a Ct C observC precedemment 163 et a 174 nm. Ces observations confirment la conclusion que I'knergie du photon est trks probablement distribuCe de f q o n statistique dans le tissu vibrationnel de la molCcule photoexcitee avant sa fragmentation. DANIELLE HOUDE, HELENE DESLAURIERS, and GUY J. COLLIN. Can. J. Chem. 61, 962 (1983).The gaseous photolysis of 3-methyl-I-butene (M3B I ) and of 2-methyl-I-butene (M2B I) has been studied at 185 nm. The observed primary fragmentation processes of the photoexcited molecules confirm the leading role of the P(C-C) bond rupture, with formation of methyl radicals and either a-methallyl radicals (M3BI system) or P-methallyl radicals (M2BI system). The comparison of the two systems suggests a very simple method to evaluate the energy content of the methallyl excited radical: 48% of C4H7* radicals so produced have an energy content of 50 ? 8 kcal mol-' at 185 nm. Other comparisons have been made with results previously obtained at 163 and 174 nm. These observations support the idea that the energy of the incident photon is very likely distributed among the vibrational frame of the photoexcited molecule before the occurrence of fragmentation processes.
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