The CCl₂ + HCl → CHCl₃ (1) insertion reaction has been investigated by ab initio molecular orbital and kinetic calculations. The geometries of reactants, products and transition state were optimized with a large number of density functional theory (DFT) formulations combined with the 6-311++G(3df,3pd) basis set. The reaction barriers calculated with G4(MP2)//DFT and G4//DFT theories of 1.16 ± 0.27 and 0.61 ± 0.26 kcal mol^-1 are consistent with the barrier height of ΔE₀^# = 1.54 ± 0.30 kcal mol^-1 estimated from the room temperature experimental rate constant. Calculated enthalpies of reaction of -53.97 ± 0.09 (G4(MP2)//DFT), -55.27 ± 0.09 (G4//DFT) and -56.52 ± 3.90 kcal mol^-1 (DFT) agree well with experimental values. The obtained rate constants over the 300 - 2000 K temperature range at the high and low pressure limit can be expressed as k_1,∞(G4(MP2)//DFT) = (4.8 ± 1.8) x 10^-14 (T/300 K)^2.12±0.19 and k_1,∞(G4//DFT) = (9.8 ± 3.4) x 10^-14 (T/300 K)^1.77±0.16 in cm³ molecule^-1 s^-1, and k_1,0 = [HCl] 3.40 x 10^-27 (T/300 K)^-6.57 exp(-2218 K/T) cm³ molecule^-1 s^-1. Falloff curves for the intermediate pressure range obtained for the reactions (1, -1) with these rate constants and a derived central broadening factor of F_cent = 0.16 + 0.84 exp(-T/331 K) + exp(-7860 K/T) were compared with reported experimental rate data.

通过从头算分子轨道和动力学计算，已经研究了CCl ₂ + HCl→CHCl ₃（1）的插入反应。使用大量的密度泛函理论（DFT）公式结合6-311 ++ G（3 df，3 pd）基础集对反应物，产物和过渡态的几何形状进行了优化。用G4（MP2）// DFT和G4 // DFT理论计算的反应势垒为1.16±0.27和0.61±0.26 kcal mol ^-1与势垒高度ΔE ₀ ^＃ = 1.54±0.30 kcal mol ^-1一致从室温估算实验速率常数。计算的-53.97±0.09（G4（MP2）// DFT），-55.27±0.09（G4 // DFT）和-56.52±3.90kcal mol ^-1（DFT）的反应焓与实验值很好地吻合。在高压和低压极限下在300-2000 K温度范围内获得的速率常数可以表示为k _1，∞（G4（MP2）// DFT）=（4.8±1.8）x 10 ^-14（T / 300 K）^2.12±0.19和k _1，∞（G4 // DFT）=（9.8±3.4）x 10 ^-14（T / 300 K）^1.77±0.16 in cm ³分子^-1 s ^-1，以及k _1,0 = [HCl] 3.40 x 10 ^-27（T / 300 K）^-6.57 exp（-2218 K / T）cm ³分子^-1 s ^-1。具有这些速率常数和派生的中心展宽因子F _cent = 0.16 + 0.84 exp（-T / 331 K）+ exp（-7860 K / T）的反应（1，-1）获得的中压范围的衰减曲线）与报告的实验速率数据进行了比较。