甲酸乙酯与羟基自由基氢提取反应速率常数的量化计算与激波管实验

针对甲酸乙酯（H（CO）OCH₂CH₃）与羟基自由基（OH）的反应动力学展开了理论与实验研究.在理论方面，首先通过量化计算得到了在M06-2x/ma-TZVP水平下准确的反应势能面，随后利用多结构-扭转（multi-stucture torsion MS-T）方法对转动非谐效应进行了研究，获得了非谐校正系数，最后基于传统过渡态理论并考虑Eckart隧穿效应获得了200~2 000 K温度范围的反应速率常数.在实验方面，开展了激波管实验来测定H（CO）OCH₂CH₃与OH的反应速率常数，基于激光吸收光谱技术探测OH自由基306.7 nm的吸收线，并对反射激波后高温反应过程的OH浓度变化进行测量，从而获得了900~1 321 K温度范围的反应速率常数，并论证了理论计算结果的合理性与准确性. 

A Combined Theoretical and Experimental Study on the Reaction Kinetics of Ethyl Formate with the Hydroxyl Radical

This work reported a theoretical and experimental study on the reaction kinetics of ethyl formate and the hydroxyl radical. Theoretically, accurate potential energy surface was calculated at the M06-2x/ma-TZVP level of theory. The torsional anharmonicity was then considered with the multi-structure torsion (MS-T) method and the corresponding torsional correction coefficients were obtained. The rate coefficients at 200~2 000 K were computed with transition state theory including the Eckart tunneling correction. Experimentally, a series of shock tube experiments at 900~1 321 K and 1.4~2.0 atm were conducted to measure the rate coefficients. In detail, laser absorption spectroscopy was employed to monitor the hydroxyl concentration at the absorption peak wavelength of 306.7 nm. The overall rate coefficients for the reaction of ethyl formate with hydroxyl radical were derived from the measured OH profiles based on a detailed kinetic model. Our calculations were validated against these experimental measurements, justifying the accuracy and rational of the theoretical predictions.