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>The kinetics of free radicals generated by IR laser photolysis. I. Reactions of C2(athinsp;3Pgr;u) with NO, vinyl cyanide, and ethylene
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The kinetics of free radicals generated by IR laser photolysis. I. Reactions of C2(athinsp;3Pgr;u) with NO, vinyl cyanide, and ethylene
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机译：The kinetics of free radicals generated by IR laser photolysis. I. Reactions of C2(athinsp;3Pgr;u) with NO, vinyl cyanide, and ethylene
C2(athinsp;3Pgr;u) molecules are produced by multiple photon dissociation of either vinyl cyanide or ethylene with the focused output from a CO2TEA laser. Their reaction with NO is reported in this paper. The total quenching rate coefficient of C2(athinsp;3Pgr;u) by NO is determined both from laser induced fluorescence of C2(athinsp;3Pgr;u) and from the time resolved chemiluminescence from CN(Bthinsp;2Sgr;+) and CN(Athinsp;2Pgr;) which are formed in the reaction, and is (7.5plusmn;0.3)10minus;11cm3moleculeminus;1secminus;1. The vibrational energy disposal within theBthinsp;2Sgr;+andAthinsp;2Pgr; states of CN is estimated from the resolved bands of the CN(Bthinsp;2Sgr;+rarr;Xthinsp;2Sgr;+) and CN(Athinsp;2Pgr;rarr;Xthinsp;2Sgr;+) emission systems. Vibrational levels of CN(Bthinsp;2Sgr;+) up to at leastvprime;=5 but lower thanvprime;=10 are excited, accompanied by high rotational excitation. CN in theAthinsp;2Pgr; state is excited to at least the 16th vibrational level. The reaction populates theAthinsp;2Pgr; state about 7 times more efficiently than it does theBthinsp;2Sgr;+state. The reaction mechanism is discussed, and it is concluded that most of the electronically excited molecules are produced via the single step reaction C2(athinsp;3Pgr;u)+NOrarr;CN(Bthinsp;2Sgr;+orAthinsp;2Pgr;)+CO(Xthinsp;1Sgr;+). Quenching rate coefficients of C2(athinsp;3Pgr;u) by vinyl cyanide and ethylene are also reported.
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