Theoretical Studies on the Mechanisms and Dynamics of OH Radical with (CH3)3COOH and (CH3)2CHOOH

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• 作者：He Ren ; Lingling Zhang ; Rongshun Wang ; Xiumei Pan
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：November 8, 2012
• 年：2012
• 卷：116
• 期：44
• 页码：10647-10655
• 全文大小：572K
• 年卷期：v.116,no.44(November 8, 2012)
• ISSN：1520-5215

文摘

A dual-level direct dynamic method is employed to study the reaction mechanism of hydroxyl radical with (CH₃)₃COOH and (CH₃)₂CHOOH. Eight hydrogen abstraction channels are found for title reactions. The energy paths are optimized at the BH&H-HLYP/6-311G(d,p) level, and the energy profiles are further refined by interpolated single-point energies method at the CCSD(T) and QCISD(T) theories. Rate coefficients for the reactions of the OH with (CH₃)₃COOH/(CH₃)₂CHOOH are computed by the canonical variational transition-state theory with the small-curvature tunneling correction between 200 and 2000 K. The Arrhenius expressions k₁ (T) = 1.49 脳 10^鈥?6 T^4.71 exp(1981.92/T) and k₂ (T) = 1.58 脳 10^鈥?0 T^3.32 exp(210.59/T) over 200鈥?000 K are obtained.