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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution
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Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution

机译：CN自由基与丙酮在溶液中反应的两种产物的振动激发

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Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: "free" (uncomplexed) CN radicals, and "solvated" CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 +/- 0.5) X 10(10) M-1 s(-1) and transient vibrational spectra in the C=N and C=O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally. excited. The rate coefficient for the reaction of solvated CN with acetone is 40 time slower than for free CN, with a rate coefficient of (2.0 +/- 0.9) X 10(9) M-1 s(-1) obtained from the rise in the HCN product v(1)(C=N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN-CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still.
机译：瞬态电子和振动吸收光谱揭示了氘化氯仿溶液中CN自由基与丙酮的双分子反应的机理和动力学。 CN自由基是通过溶解的ICN的超快紫外光解产生的。 CN自由基的两种反应形式以其电子吸收带为特征：“游离”（未络合）CN自由基和与溶剂分子络合的“溶剂化” CN自由基。自由基CN自由基的光解产生后，其寿命被限制在几皮秒内，这是因为它们会重新结合成ICN和INC，与CDCl3分子络合以及与丙酮反应。丙酮反应的速率系数为（8.0 +/- 0.5）X 10（10）M-1 s（-1），在C = N和C = O拉伸区域的瞬态振动光谱表明，新生的HCN和2-氧丙基（CH3C（O）CH2）自由基产物是振动的。兴奋。溶剂化的CN与丙酮反应的速率系数比游离的CN慢40倍，速率系数为（2.0 +/- 0.9）X 10（9）M-1 s（-1）。 HCN乘积v（1）（C = N拉伸）IR吸收带。还提供了具有丙酮的CN络合物的证据，由于CN与羰基的相互作用，该络合物比CN-CDCl3络合物的结合更牢固。这些更紧密缔合的基团的反应速率仍然较慢。

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