Computational study on the mechanisms and kinetics of the CH(2)BrO(2) + ClO reaction in the atmosphere.
Computational study on the mechanisms and kinetics of the CH(2)BrO(2) + ClO reaction in the atmosphere.
复制标题
大气中CH2BrO2 ClO反应机理和动力学的计算研究
作者：
在CCSD（T）/cc-pVTZ//B3 LYP/6-311++G（d，p）水平上研究了CH 2BrO 2 + ClO反应的单重态和三重态势能面.在三重态势能面上，CH 2BrO 2与ClO的反应主要通过SN 2置换和吸氢两种反应机理进行，其中吸氢生成P3（CHBrO 2 + HOCl）是主要反应机理.单重态PES存在加成/消除和SN 2置换机制，且更为复杂。对CH 2BrO 2 + ClO反应机理和产物分布的RRKM计算表明，在T ≤ 600 K时，IM 1（CH 2BrOOOBr）的稳定作用占主导地位，而在T > 600 K时，P1（CHBrO + HO 2 + Cl）的生成途径占据了整个反应.总速率常数与压力无关，而单个速率常数对压力敏感。在ClO存在下，CH_2BrO_2的寿命为20.27 h。含时密度泛函理论（TDDFT）计算表明，IM 1（CH 2BrOOOCl）、IM 2（CH 2BrOOClO）和IM 3（CH 2BrOClO 2）在太阳光照射下发生光解.在CCSD（T）/cc-pVTZ//B3 LYP/6-311++G（d，p）水平上研究了CH 2BrO 2 + ClO反应的单重态和三重态势能面.
The singlet and triplet potential energy surfaces for the CH2BrO2 + ClO reaction are studied at the CCSD(T)/cc-pVTZ//B3LYP/6-311++G(d,p) level. CH2BrO2 is revealed to react with ClO through two kinds of mechanisms on the triplet potential energy surface (PES), namely, SN2 displacement and H-abstraction, and the production of P3 (CHBrO2 + HOCl) via H-abstraction is the dominant channel. Addition/elimination and SN2 displacement mechanisms exist on the singlet PES and are more complicated. The RRKM calculations of the mechanism and product distribution in the CH2BrO2 + ClO reaction show that the stabilization of IM1 (CH2BrOOOBr) is dominant at T ≤ 600 K, while the pathway of producing P1 (CHBrO + HO2 + Cl) occupies the entire reaction at T > 600 K. The total rate constants are independent of pressure, while the individual rate constants are sensitive to pressure. The lifetime of CH2BrO2 in the presence of ClO is estimated to be 20.27 h. Moreover, time-dependent density functional theory (TDDFT) calculations suggest that IM1 (CH2BrOOOCl), IM2 (CH2BrOOClO) and IM3 (CH2BrOClO2) will photolyze under the sunlight. The singlet and triplet potential energy surfaces for the CH2BrO2 + ClO reaction are studied at the CCSD(T)/cc-pVTZ//B3LYP/6-311++G(d,p) level.
登录
查看更多内容
影响因子：
2.9
作者：
Hou, H;Wang, BS;Gu, YS
通讯作者：
Gu, YS
影响因子：
2.8
作者：
RAGHAVACHARI, K;TRUCKS, GW;HEADGORDON, M
通讯作者：
HEADGORDON, M
影响因子：
--
作者：
GONZALEZ, C;SCHLEGEL, HB
通讯作者：
SCHLEGEL, HB
影响因子：
4.4
作者：
ASTHOLZ, DC;TROE, J;WIETERS, W
通讯作者：
WIETERS, W
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD