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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical study of the mechanism of NO2 production from NO plus CIO
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Theoretical study of the mechanism of NO2 production from NO plus CIO

机译：NO + CIO产生NO2机理的理论研究

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摘要

The reaction of NO with ClO has been studied theoretically using density-functional and wave function methods (B3LYP and CCSD(T)). Although a barrier for cis and trans additions could be located at the RCCSD(T) and UCCSD(T) levels, no barrier exists at the B3LYP/6-311+G(d) level. Variational transition state theory on a CASPT2(12,12)/ANO-L//B3LYP/6-311+G(d) surface was used to calculate the rate constants for addition. The rate constant for cis addition was faster than that for trans addition (cis:trans 1:0.76 at 298 K). The rate constant data summed for cis and trans addition in the range 200-1000 K were fit to a temperature-dependent rate in the form k(dis) = 3.30 x 10(-13) T-0.5881 exp(305/T) cm(3) . molecule(-1) .s(-1), which is in good agreement with experiment. When the data are fit to an Arrhenius plot in the range 200-400 K, an activation barrier of -0.35 kcal/mol is obtained. The formation of CINO2 from ONOCl has a much higher activation enthalpy from the trans isomer compared to the cis isomer. In fact, the preferred decomposition pathway from trans-ONOCl to NO2 + Cl is predicted to go through the cis-ONOCl intermediate. The trans -> cis isomerization rate constant is k(iso) = 1.92 x 10(13) exp(-4730/T) s(-1) using transition state theory.
机译：使用密度泛函和波函数方法（B3LYP和CCSD（T））从理论上研究了NO与ClO的反应。尽管顺式和反式添加的障碍可能位于RCCSD（T）和UCCSD（T）级别，但B3LYP / 6-311 + G（d）级别不存在障碍。使用CASPT2（12,12）/ ANO-L // B3LYP / 6-311 + G（d）表面的变迁过渡态理论来计算加料速率常数。顺式加成的速率常数比反式加成的速率常数快（在298 K时，顺式：反式1：0.76）。将200-1000 K范围内的顺式和反式加法求和的速率常数数据与温度相关速率拟合为k（dis）= 3.30 x 10（-13）T-0.5881 exp（305 / T）cm （3）。分子（-1）.s（-1），与实验吻合良好。当数据适合200-400 K范围内的Arrhenius图时，可获得-0.35 kcal / mol的活化势垒。与顺式异构体相比，由ONOC1形成的CINO2具有来自反式异构体的更高的活化焓。实际上，预计从反式-ONOCl到NO2 + Cl的优选分解途径将通过顺式-ONOCl中间体。使用过渡态理论，反式->顺式异构化速率常数为k（iso）= 1.92 x 10（13）exp（-4730 / T）s（-1）。

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