KF_4^-和KF_4系列超卤化物稳定性及热裂解的理论研究

Theoretical studies on the stabilities and pyrolysis of KF_4^- and KF_4 hyperhalogen compounds series

目的对KFn-和KFn(n=1～4)系列超卤化物进行理论研究。方法采用密度泛函理论B3LYP/6-311+G(3df)方法。结果得到了KF n-和KFn系列卤化物的稳定构型、垂直电离能VDE、垂直电子亲合能EAvert、绝热电子亲合能EAad、同位素效应及裂解反应热力学信息。结论同位素效应不影响VDE,EAvert,EAad及裂解反应热力学能变的值。中性物质每一步的裂解均易于其负离子的对应裂解。相对电离而言,热裂解更容易破坏该类负离子。

Aim To study KFn- and KFn （ n = 1 - 4 ） hyperhalogen compounds. Methods By applying Density Functional Theory （DFT） B3LYP/6 - 311 ＋ G （3df） method. Results The equilibrium structures, vertical detachment energies （VDE）, vertical electron affinities （EAvert ）, adiabatic electron affinities （EAad）, isotope effect and pyrolysis thermodynamics were obtained. Conclusion The isotope effect does not influence VDE, EAvert, EAad and the thermodynamics energy changes of pyrolysis reactions. The pyrolysis of neutral hyperhalogens is easier than their anion＇s, and pyrolysis rather than ionization is likely the easiest way of destroying these anions.