HONO与CH_3·反应机理的理论研究
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摘要
采用密度泛函理论和耦合簇理论等方法研究了HONO与CH_3·的反应机理.在B3PW91/6-311G(d,p)方法下,优化了反应势能面上的反应物、中间体、过渡态和产物的几何构型;通过内禀反应坐标(IRC)确认了反应物、过渡态、中间体和产物之间的相关性.利用CCSD(T)/aug-cc-pVTZ方法计算了各驻点单点能量,并拟合计算了反应速率常数.计算结果表明,HONO与CH_3·的主要反应通道为cis-HONO+CH_3·→cis-IMA1→cis-TSA1→cisIMA2,其产物为NO_2和CH_4.
The mechanism of reaction between HONO and CH_3·was investigated by the means of DFT and CCSD.The geometrical parameters of the reactants,transition states,intermediates and products were optimized at the B3 PW91/6-311 G(d,p)computational level.Based on the optimized geometries,the reactants,transition states,intermediates and products were detected by frequency analysis.The intrinsic reaction coordinates(IRC)were traced and connecting relationships between the reactants,intermediates,transition states and products were confirmed.The reliable single point energies of the species were computed by employing the CCSD(T)/aug-cc-pVTZ method,and the reaction rate constants were exponential fitted.The result shows that the dominant reaction channel is cisHONO+CH_3·→cis-IMA1→cis-TSA1→cis-IMA2,and the major products are NO_2 and CH_4.
The mechanism of reaction between HONO and CH_3·was investigated by the means of DFT and CCSD.The geometrical parameters of the reactants,transition states,intermediates and products were optimized at the B3 PW91/6-311 G(d,p)computational level.Based on the optimized geometries,the reactants,transition states,intermediates and products were detected by frequency analysis.The intrinsic reaction coordinates(IRC)were traced and connecting relationships between the reactants,intermediates,transition states and products were confirmed.The reliable single point energies of the species were computed by employing the CCSD(T)/aug-cc-pVTZ method,and the reaction rate constants were exponential fitted.The result shows that the dominant reaction channel is cisHONO+CH_3·→cis-IMA1→cis-TSA1→cis-IMA2,and the major products are NO_2 and CH_4.
引文
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