Theoretical Study on the Gas Phase Reaction of Allyl Alcohol with Hydroxyl Radical

详细信息    查看全文

• 作者：Yunju Zhang ; Kai Chao ; Jingyu Sun ; Zhongmin Su ; Xiumei Pan ; Jingping Zhang ; Rongshun Wang
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：August 1, 2013
• 年：2013
• 卷：117
• 期：30
• 页码：6629-6640
• 全文大小：678K
• 年卷期：v.117,no.30(August 1, 2013)
• ISSN：1520-5215

文摘

The complex potential energy surface of allyl alcohol (CH₂CHCH₂OH) with hydroxyl radical (OH) has been investigated at the G3(MP2)//MP2/6-311++G(d,p) level. On the surface, two kinds of pathways are revealed, namely, direct hydrogen abstraction and addition/elimination. Rice-Ramsperger-Kassel-Marcus theory and transition state theory are carried out to calculate the total and individual rate constants over a wide temperature and pressure region with tunneling correction. It is predicted that CH₂CHOHCH₂OH (IM1) formed by collisional stabilization is dominate in the temperature range (200鈥?40 K) at atmospheric pressure with N₂ (200鈥?15 K at 10 Torr Ar and 100 Torr He). The production of CH₂CHCHOH + H₂O via direct hydrogen abstraction becomes dominate at higher temperature. The kinetic isotope effect (KIE) has also been calculated for the title reaction. Moreover, the calculated rate constants and KIE are in good agreement with the experimental data.