三氟化氯和水反应的密度泛函理论研究

Theoretical Study on the Reaction of Chlorine Trifluoride with Water by Density Functional Theory

应用量子化学密度泛函理论(DFT),对ClF3和H2O在不同比例下的反应进行了研究.在B3pw91/6-31++G(d,p)水平上优化了反应物、中间体、过渡态和产物的几何构型,计算出它们的振动频率和零点振动能(ZPVE),并对能量进行了校正.计算结果表明,ClF3和H2O的反应能垒很低,反应极易进行;水足量有利于生成HClO2,少量有利于生成其它卤氧化合物.

Using the density functional theory （DFT）, the reaction of chlorine trifluoride with water of different proportion was studied. At B3pw91/6-31＋＋G（d,p） level with DFT method, the geometries of all species（reactants, transition states and products） were optimized and the vibration frequencies and zero point vibration energies （ZPVE） were also calculated. All the energies of the species were obtained with the correction of ZPVE. The results of the calculations showed that the energy barriers of the reaction of chlorine trifluoride and water were very low; plenty water was in favor of HClO2, insufficient water was in favor of other haloid oxide.