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首页> 外文期刊>Chemical Physics: A Journal Devoted to Experimental and Theoretical Research Involving Problems of Both a Chemical and Physical Nature >The collisional quenching of CCl_2(A ~1B_1 and a ~3B_1) by substituted methane molecules
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The collisional quenching of CCl_2(A ~1B_1 and a ~3B_1) by substituted methane molecules

机译：取代的甲烷分子对CCl_2（A〜1B_1和〜3B_1）的碰撞猝灭

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摘要

CCl_2 free radical was produced by a pulsed dc discharge of CCl_4 (in Ar). Ground electronic state CCl_2(X) radical was electronically excited to A~1B_1(0,4,0) vibronic state with Nd:YAG laser pumped dye laser at 541.52 nm. Experimental quenching data of excited CCl_2(A~1B_1 and a~3B_1) by CH_4, CH_3NO_2, CH_3OH, and halomethanes were obtained by observing time-resolved total fluorescence signal of the excited CCl_2 radical in a cell, which shows a superposition of two exponential decay components under the presence of a quencher. The quenching rate constants K_A of CCl_2 (A) state and K_a of CCl_2 (a) state were derived by analyzing the experimental data according to a proposed three-level model to deal with the CCl_2(X~1A_1, A~1B_1, a~3B_1) system. K_A and K_a increase on the whole with increasing the number of C-Cl bonds in chloromethane molecules. The formation cross sections of complexes between CCl_2(A~1B_1) radicals and CH_4, CH_3Cl, CH_3OH and CH_3NO_2 molecules were calculated by means of a collision complex model.
机译：CCl_2自由基是由CCl_4（在Ar中）的脉冲直流放电产生的。用Nd：YAG激光泵浦染料激光器在541.52 nm处将基态电子态CCl_2（X）自由基电子激发为A〜1B_1（0,4,0）振动态。通过观察细胞中受激CCl_2自由基的时间分辨总荧光信号，获得了CH_4，CH_3NO_2，CH_3OH和卤代甲烷对受激CCl_2（A〜1B_1和a〜3B_1）的实验猝灭数据，该结果显示了两个指数的叠加在淬灭剂的存在下衰减组分。根据提出的三能级模型对实验数据进行分析，得到CCl_2（A）态的猝灭速率常数K_A和CCl_2（a）态的猝灭常数K_a，以处理CCl_2（X〜1A_1，A〜1B_1，a〜 3B_1）系统。随着氯甲烷分子中C-Cl键数量的增加，K_A和K_a总体上增加。利用碰撞配合物模型计算了CCl_2（A〜1B_1）自由基与CH_4，CH_3Cl，CH_3OH和CH_3NO_2分子之间的配合物形成截面。

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