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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Unimolecular Dissociation of Formyl Halides HXCO → CO + HX (X = F, Cl): An Ab Initio Direct Classical Trajectory Study
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Unimolecular Dissociation of Formyl Halides HXCO → CO + HX (X = F, Cl): An Ab Initio Direct Classical Trajectory Study

机译：甲酰卤HXCO→CO + HX（X = F，Cl）的单分子解离：从头开始直接经典轨迹研究

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摘要

The dynamics of the unimolecular dissociation of formyl halides, HXCO (X = F, Cl), have been studied by classical trajectory calculations at the MP2/6-31G(d,p) level of theory and have been compared to similar calculations for H_2CO. The calculated transition states are planar with elongated C-X and H-X bonds. Trajectories were started from the transition state with 12 kcal/mol of energy above the potential barrier, corresponding to the zero-point energy plus 2.25 and 2.87 kcal/mol of excess energy in the transition vector of formyl fluoride and formyl chloride, respectively. The CO fragments are produced rotationally hot with = 40-50 but vibrationally cold with only 10-20% in v = 1. The HX fragment shows significant vibrational excitation with = 1.0 for HF and = 2.3 for HCl, compared to = 1.16 for H_2. The average rotational quantum number for HCl, = 12.8, is considerably higher than for HF, = 9.5, or H_2, = 3.3. Product translation receives about 42% of the available energy in formyl fluoride and about 31% in formyl chloride compared to 70% for formaldehyde. The results show good qualitative agreement with the available experimental energy partitioning for HFCO; HF is observed to be vibrationally hot, but the distribution has not been measured. No experiments are available for HClCO dissociation.
机译：通过MP2 / 6-31G（d，p）理论水平的经典轨迹计算研究了甲酰卤的单分子解离动力学HXCO（X = F，Cl），并已与H_2CO的类似计算进行了比较。计算得到的过渡态是平面的，带有细长的C-X和H-X键。轨迹从过渡态开始，在势垒上方有12 kcal / mol的能量，分别对应于零点能量加上甲酰氟和甲酰氯的过渡矢量中的2.25和2.87 kcal / mol过量能量。 CO片段旋转加热产生， = 40-50，振动产生冷，在v = 1时仅占10-20％。HX片段显示出显着的振动激发，HF的 = 1.0和 = 2.3 HCl，而H_2的 = 1.16。 HCl的平均旋转量子数 = 12.8，远高于HF的平均旋转量子数， = 9.5或H_2， = 3.3。与甲醛的70％相比，产物转化在甲酰氟中获得约42％的可用能量，在甲酰氯中获得约31％的可用能量。结果表明，与HFCO可用的实验能量分配具有良好的定性一致性。观察到HF振动热，但尚未测量其分布。没有可用于HClCO解离的实验。

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