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本文采用CCSD(T)/aug-cc-pVTZ//UB3LYP/6-311+G(2d,p)方法对HCl+NO_3反应机理及速率常数进行了研究,并在此基础上考虑了水分子对该反应的影响。研究结果表明,HCl+NO_3反应经历了生成产物为Cl+HNO_3的通道,克服了13.67kcal·mol~(-1)的能垒。加入水分子后,所得的产物并没有发生改变,但势能面却比裸反应复杂得多,经历了NO_3…H_2O+HCl、H_2O…HCl+NO_3和HCl…H_2O+NO_3三条反应通道。其中通道HCl…H_2O+NO_3为水分子参与反应的优势通道。此外,该通道比相同温度下裸反应的速率常数k_(R1)提高了0.33×10~4~1.07×10~7倍,且在298K时,k’_(RW3)/k’_(total)已达到95.9%,说明此时在实际大气环境中水分子对NO_3+HCl反应有明显的影响。
In this paper, the reaction mechanism and rate constants of HCl + NO 3 have been studied by CCSD (T) / aug-cc-pVTZ // UB3LYP / 6-311 + G (2d, p) The effect of this reaction. The results show that the reaction of HCl + NO 3 undergoes the passage of Cl + HNO 3 to overcome the energy barrier of 13.67 kcal · mol -1. After the addition of water molecules, the obtained product has not changed, but the potential energy surface is much more complicated than the bare reaction and has gone through three reaction channels of NO_3 ... H_2O + HCl, H_2O ... HCl + NO_3 and HCl ... H_2O + NO_3. Among them, channel HCl ... H_2O + NO_3 is the dominant channel for water molecules to participate in the reaction. In addition, the channel constant k_ (R1) increased by 0.33 × 10 ~ 4 ~ 1.07 × 10 ~ 7 times higher than that of bare reaction at the same temperature, and k ’_ (RW3) / k’ Has reached 95.9%, indicating that at this time in the actual atmospheric water molecules on the NO_3 + HCl reaction has a significant impact.