ClF_3O与H_2O反应机理的密度泛函理论研究

应用量子化学密度泛函理论对ClF3O和H2O的反应机理进行了研究。在B3PW91/6-31++G(d,p)水平上优化了反应通道上的反应物、中间体、过渡态和产物的几何构型,计算了它们的振动频率和零点能,并对能量进行了零点能校正(E+ZVPE就是对能量进行了零点能校正的值),找到了反应通道。结果表明:ClF3O和H2O极易发生反应,水足量时有利生成HF、HClO2和HClO4;水少量时有利于生成HF和ClFO。

Reaction Mechanism of Chlorine Trifluoride Oxide and Water with Density Functional Theory

Using density functional theory (DFT), the reaction of chlorine trifluoride oxide with water was studied. At the B3PW91/6-31+ G(d,p) level of DFT, the geometries of reactants, transition states, and products were optimized and the vibration frequencies and zero point vibrational energies (ZPVE) were calculated. Their energies were obtained with the correction of ZPVE. Results show that the energy barriers of the reaction of chlorine trifluoride oxide and water are very low, and a plenty of water is in favor of producing HF, HClO₂ and HClO₄, however, insufficient water is in favor of producing HF and ClFO₂.