Zhou Yujie, Cao Qi, Yang Yu, Ma Dandan, Zhu Quan, Ma Jianyi
Institute of Atomic and Molecular Physics, Sichuan University Chengdu 610065 China
Reactor Operation and Application Research Sub-Institute, Nuclear Power Institute of China Chengdu 610041 China.
RSC Adv. 2022 Sep 30;12(43):28010-28019. doi: 10.1039/d2ra04931g. eCollection 2022 Sep 28.
We studied the effect of water clusters on the NH + OH reaction at both the DFT and CCSD(T) levels. The calculated rate constants for the pure reaction are 2.07 × 10 and 1.35 × 10 cm molecule s in the gas and liquid phases, respectively, and the gas-phase rate constants are consistent with the corresponding experimental result (1.70 × 10 cm molecule s), while the liquid-phase rate constants are slightly smaller than the experimental value (5.84 × 10 cm molecule s). In the gas phase, the presence of (HO) ( = 1-3) decreases the rate constant compared to the pure NH + OH reaction, and these results are in agreement with many reported HO-catalyzed reactions. For the liquid phase reaction, compared with the case of = 0-3, when the size of the water molecule cluster surrounding the OH radical is = 13, the rate constant of the title reaction increases. Our study also shows that proton transfer is also a factor which accelerates the liquid phase NH + OH reaction.
我们在密度泛函理论（DFT）和耦合簇单双激发（CCSD(T)）水平上研究了水簇对NH + OH反应的影响。纯反应在气相和液相中的计算速率常数分别为2.07×10和1.35×10 cm³·分子⁻¹·s⁻¹，气相速率常数与相应的实验结果（1.70×10 cm³·分子⁻¹·s⁻¹）一致，而液相速率常数略小于实验值（5.84×10 cm³·分子⁻¹·s⁻¹）。在气相中，与纯NH + OH反应相比，(HO)ₙ（n = 1 - 3）的存在降低了速率常数，这些结果与许多报道的HO催化反应一致。对于液相反应，与n = 0 - 3的情况相比，当围绕OH自由基的水分子簇大小为n = 13时，标题反应的速率常数增加。我们的研究还表明，质子转移也是加速液相NH + OH反应的一个因素。
