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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanistic insights into NO3 center dot induced self-terminating radical oxygenations, Part 1: A computational study on NO3 center dot and its addition to alkynes
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Mechanistic insights into NO3 center dot induced self-terminating radical oxygenations, Part 1: A computational study on NO3 center dot and its addition to alkynes

机译：对NO3中心点诱导的自终止自由基氧合的机理研究，第1部分：NO3中心点及其在炔烃中的添加的计算研究

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摘要

The geometry of the nitrate radical, NO3center dot, for which unrestricted Hartree-Fock (HF) breaks spatial symmetry of the wave function, was optimized using hybrid density functionals that include varying fractions of Hartree-Fock exchange. Although symmetry breaking was not observed even when the functional with the highest HF exchange (BHandHLYP) was used, only B3LYP correctly describes the D-3h symmetry of NO3center dot as groundstate structure with the lowest energy. Further, geometries and energies of the stationary points in the addition of NO3center dot to ethyne, propyne, and 2-butyne were calculated using ab initio and density functional methods. The reactions proceed through Z-configurated transition states leading to Z-configurated vinyl radicals with the activation barrier decreasing with increasing methyl substitution at the C equivalent to C triple bond by ca. 11 kJ mol(-1) per methyl group. It was found that the results obtained at the BHandHLYP/cc-pVDZ level of theory are in good agreement with the data from sincyle-point QCISD and CCSD(T) calculations.
机译：使用混合密度泛函函数（包括不同比例的Hartree-Fock交换）优化了硝酸根自由基，NO3中心点的几何形状，无限制的Hartree-Fock（HF）打破了该函数的空间对称性。尽管即使使用具有最高HF交换的官能团（BHandHLYP）也未观察到对称性破坏，但只有B3LYP正确地将NO3中心点的D-3h对称性描述为能量最低的基态结构。此外，使用从头算和密度泛函方法计算了向乙炔，丙炔和2-丁炔中添加NO3中心点后固定点的几何形状和能量。反应通过Z-构型的过渡态进行，导致Z-构型的乙烯基自由基，其活化势垒随着在C上相当于C-三键的C上甲基取代的增加而降低。每个甲基11 kJ mol（-1）。发现在BHandHLYP / cc-pVDZ理论水平上获得的结果与单点QCISD和CCSD（T）计算得出的数据非常吻合。

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