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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Time-resolved kinetic studies on quenching of HCF(A(1)A '') by alkane and alcohol molecules
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Time-resolved kinetic studies on quenching of HCF(A(1)A '') by alkane and alcohol molecules

机译：烷烃和醇分子淬灭HCF（A（1）A''）的时间分辨动力学研究

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摘要

HCF((X) over tildeA') radicals were produced by laser photolysis of CHFBr2 at 213 nm and were electronically excited from the ground state to A(1)A"(030) at 492.7 nm with a dye laser pumped by a Nd:YAG laser. With the analysis of the lifetime of the time-resolved total fluorescence signals collected in the reaction cell where the total pressure was fixed to be 14.0 Torr, the quenching data of HCF((A) over tildeA") by alkane and alcohol molecules at room temperature were derived from variation of pseudo-first-order rate constant with different quencher pressures. It is found that the quenching rate constants are close to the collision rate constants (10(-10) cm(3) molecule(-1) s(-1)), indicating the long-range attractive forces between the collision partners play an important role in the entrance channel of quenching process. Several kinetic models were applied to analyze the mechanism of the quenching process. The complex formation cross sections are calculated with the collision complex model. Correlations of the quenching rate constant for the removal of the HCF((A) over tilde (1)A") state with ionization potential of the quenching partners show that the insertion reactive mechanism is probably the dominant reaction channel, which is analogous to the behaviors of other three-atom carberies in corresponding electronic states.
机译：通过在213 nm处对CHFBr2进行激光光解来产生HCF（在tildeA'上的（X）自由基，并用Nd泵浦的染料激光将其从基态电子激发到492.7 nm的基态至A（1）A“（030）： YAG激光器。分析了在总压力固定为14.0 Torr的反应池中收集的时间分辨的总荧光信号的寿命，利用烷烃和醇淬灭HCF（（A）超过tildeA“）的数据室温下的分子是由不同的淬灭剂压力下的拟一级反应速率常数的变化得出的。发现猝灭速率常数接近碰撞速率常数（10（-10）cm（3）分子（-1）s（-1）），表明碰撞伙伴之间的长距离吸引力起着在淬火过程的入口通道中起重要作用。应用了几种动力学模型来分析淬火过程的机理。复杂地层横截面是通过碰撞复杂模型计算的。消除波浪号（1）A“）上的HCF（（A））状态的淬灭速率常数与淬灭伙伴的电离势的相关性表明，插入反应机理可能是主要的反应通道，类似于其他三原子碳原子在相应电子状态下的行为。

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