Zhang Weichao, Du Benni, Qin Zhenglong
College of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University , Xuzhou, Jiangsu 221116, People's Republic of China.
J Phys Chem A. 2014 Jul 3;118(26):4797-807. doi: 10.1021/jp502886p. Epub 2014 Jun 23.
In this paper, for the hydrogen abstraction reaction of HCHO by OH radicals assisted by water, formic acid, or sulfur acid, the possible reaction mechanisms and kinetics have been investigated theoretically using quantum chemistry methods and transition-state theory. The potential energy surfaces calculated at the CCSD(T)/6-311++G(df,pd)//MP2(full)/6-311++G(df,pd) levels of theory reveal that, due to the formation of strong hydrogen bond(s), the relative energies of the transition states involving catalyst are significantly reduced compared to that reaction without catalyst. However, the kinetics calculations show that the rate constants are smaller by about 3, 9, or 10 orders of magnitude for water, formic acid, or sulfur acid assisted reactions than that uncatalyzed reaction, respectively. Consequently, none of the water, formic acid, or sulfur acid can accelerate the title reaction in the atmosphere.
本文采用量子化学方法和过渡态理论，对水、甲酸或硫酸辅助下OH自由基与甲醛的氢提取反应的可能反应机理和动力学进行了理论研究。在CCSD(T)/6-311++G(df,pd)//MP2(full)/6-311++G(df,pd)理论水平下计算的势能面表明，由于强氢键的形成，与无催化剂反应相比，涉及催化剂的过渡态的相对能量显著降低。然而，动力学计算表明，水、甲酸或硫酸辅助反应的速率常数分别比无催化反应小约3、9或10个数量级。因此，水、甲酸或硫酸均不能加速大气中的该标题反应。
