Mechanism for OH-initiated atmospheric oxidation of the organophosphorus insecticide phorate
Mechanism for OH-initiated atmospheric oxidation of the organophosphorus insecticide phorate
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有机磷杀虫剂甲拌磷的 OH 引发大气氧化机制
DOI：
10.1007/s11224-013-0287-0
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发表时间：
2014-02
影响因子：
1.7
通讯作者：
Wang, Wenxing
中科院分区：
文献类型：
--
作者：
Ding, Lei;Sun, Xiaoyan;Zhang, Qingzhu;Wang, Wenxing
甲拌磷是一种极其危险的有机磷杀虫剂，目前仍在许多国家和地区广泛使用。它可能被释放到大气中，在大气中它可能发生迁移和化学变化。研究了OH引发甲拌磷常压氧化的反应机理。在6- 31 G（d，p）基组下，在MPWB 1 K水平上计算了所有驻点的几何参数和振动频率。在MPWB 1 K/6-311+G（3df，2 p）水平上进行了单点能量计算。采用具有小曲率隧穿贡献的正则变分过渡态理论计算了200-370 K温度范围内的速率常数。拟合了阿耳忒弥斯公式。结果表明，甲拌磷氧磷的形成渠道，从OH加成甲拌磷，和H提取的-CH 2-部分的甲拌磷中的-CH 2 CH 3基团的能量是有利的。主要降解产物为甲拌磷、SO2。
Phorate, an extremely hazardous organophosphorus insecticide, is still widely used in many countries and territories currently. It may be released in the atmosphere where it can undergo transport and chemical transformations. In this study, the reaction mechanism for the OH-initiated atmospheric oxidation of phorate was investigated. The geometrical parameters and vibrational frequencies of all the stationary points were calculated at the MPWB1K level with the 6-31G(d,p) basis set. Single-point energy calculations were carried out at the MPWB1K/6-311+G(3df,2p) level. Canonical variational transition-state theory with small curvature tunneling contribution was used to calculate the rate constants over the temperature range of 200–370 K. The Arrhenius formulas were fitted. The results indicate that the channel of the formation of phorate oxon resulting from OH addition to phorate, and H abstractions from the –CH2– portion of the –CH2CH3group in phorate are energetically favorable. The main degradation products include phorate oxon, SO2.
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影响因子：
4.4
作者：
Becke, AD
通讯作者：
Becke, AD
DOI：
10.1021/jp056117x
发表时间：
2006-01
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
A. Galano;A. Cruz-Torres;J. R. Álvarez-Idaboy
通讯作者：
A. Galano;A. Cruz-Torres;J. R. Álvarez-Idaboy
影响因子：
11.4
作者：
Qingzhu Zhang;X. Qu;Hui Wang;Fei Xu;Xiangyang Shi;Wen-xing Wang
通讯作者：
Qingzhu Zhang;X. Qu;Hui Wang;Fei Xu;Xiangyang Shi;Wen-xing Wang
影响因子：
4.4
作者：
Adamo, C;Barone, V
通讯作者：
Barone, V
DOI：
10.1016/j.scitotenv.2011.10.063
发表时间：
2012
期刊：
The Science of the total environment
影响因子：
--
作者：
Jia-Qi Shi;Ruijuan Qu;A. Flamm;Hong-Xia Liu;Ying Xu;Zunyao Wang
通讯作者：
Jia-Qi Shi;Ruijuan Qu;A. Flamm;Hong-Xia Liu;Ying Xu;Zunyao Wang