【摘 要】
：
异丁烯醛(MACR)是异戊二烯的主要降解产物之一[1],Cl原子与异丁烯醛的反应对异戊二烯的降解过程有着不容忽视的作用.但是到目前为止,关于该反应的能量和动力学特征没有相关文献报道.本文通过建立二维势能面的方法确定了Cl原子无能垒加成到MACR的C=C双键过程的极小能量路径和Cl原子直接提取醛基H原子的极小能量路径.沿着反应的极小能量路径,Cl原子加成到C=C双键的末端碳原子上形成端碳加成中间体,
【机 构】
：
北京理工大学化学学院,北京海淀区中关村南大街5号,100081;石家庄学院化工学院,石家庄市高新技术开发区长江大道6号,050035
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异丁烯醛(MACR)是异戊二烯的主要降解产物之一[1],Cl原子与异丁烯醛的反应对异戊二烯的降解过程有着不容忽视的作用.但是到目前为止,关于该反应的能量和动力学特征没有相关文献报道.本文通过建立二维势能面的方法确定了Cl原子无能垒加成到MACR的C=C双键过程的极小能量路径和Cl原子直接提取醛基H原子的极小能量路径.沿着反应的极小能量路径,Cl原子加成到C=C双键的末端碳原子上形成端碳加成中间体,而中心碳加成中间体只能由端碳加成中间体异构化得到.利用变分过渡态理论和主方程方法计算了反应的动力学性质.结果表明,297 K下,该反应的总速率常数为koverall = 2.3 × 10-10 cm3 molecule-1 s-1；加成反应以端碳加成为主；压力P ＜ 10 Torr时,反应是压力相关的,速率常数随压力增加而增大,反应的高压极限约为100 Torr.计算结果能够很好地解释实验现象[2].
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