| HNO与O自由基反应的密度泛函理论研究 |
| Theoretical Study on the Reaction of HNO with O Radical with Density Functional Theory |
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| 摘要: 用密度泛函理论(DFT)和从头算方法，对HNO与O自由基反应进行了研究。在(U)B3LYP/6-311G**和(U)B3LYP/aug-cc-pVTZ水平下优化了反应通道上各驻点(反应物、中间体、过渡态及产物)的几何构型。在(U)QCISD/aug-cc-pVTZ水平下计算了各物种的单点能，并对总能量进行了零点能校正。研究结果表明，HNO与O自由基反应过程中存在O → N、O → O和O → H进攻的竞争机制，且存在着多条反应通道。采用过渡态理论计算了600～2 000 K温度范围内3条慢反应通道的速率常数。求得lnk和1/T之间的线性关系。3种通道的阿累尼乌斯指前因子分别为1.469 × 1010、1.22 × 1010(1.06 × 1010)和2.26 × 1013。 |
| 关键词: 密度泛函理论 HNO+O 反应通道 反应速率 |
| 基金项目: |
| Abstract: The reaction of HNO with O radical was investigated by density functional theory (DFT) and ab initio methods. The stationary points on the reaction paths (reactants, intermediates and products) were optimized at the (U)B3LYP/6-311G** and (U)B3LYP/aug-cc-pVTZ levels. Single-point calculations were performed at the (U)QCISD/aug-cc-pVTZ level for the optimized structures and all the total energies were corrected by the zero-point energy. It was shown that there exist three competing mechanisms of oxygen attacking nitrogen O → N, oxygen attacking oxygen O → O and oxygen attacking hydrogen O → H and plenty of reaction channels during the reaction of HNO with O. The rate constants were obtained via Eyring transition-state theory in temperature range of 600～2 000 K. The linear relationship between lnk and 1/T was presented. The frequency factors in the Arrhenius formula for the three reaction paths are 1.469 × 1010, 1.22 × 1010(1.06 × 1010) and 2.26 × 1013, respectively. |
| Keywords: density functional theory HNO+O reaction channel reaction rate |
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| 黄玉成,居学海,邱玲,肖鹤鸣.HNO与O自由基反应的密度泛函理论研究[J].无机化学学报,2006,22(11):1962-1966. |
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