Geometrical structure of PF, and PFJ (n=l~6) is optimized and their electronic structure is studied using high level ab-inito methods. The results show that the electrons in PF3 ,PF5 and PF2- ,PF4-, PF6- form closed shell and these species are very stable; PF3- is unstable as it's energy is higher than the corresponding neutral; the structures of PF5- and PF5 are quite different, and the VEA of PF5 is negative? PFf can't be formed through catching an electron by PF5; PF6 is not stable, but PF6- and PF4- are the most stable anions according to the average bond strength. These results are in agreement with the anion intensity produced by Cs+ sputtering on KPF6.%对PFn和PF-n(n=1～6)的基态结构进行了高精度的理论计算,得到了它们的结合能和中性分子的电子亲和势,分析了它们的电子结构.结果表明,中性PF3,PF5分子和阴离子PF-2,PF-4,PF-6中电子形成稳定的闭壳层结构,比较稳定,PF3不能形成阴离子；虽然PF5的绝热电子亲和势为正,但垂直电子亲和势为负,PF5不能直接俘获电子形成阴离子；PF6不稳定,但PF-6与PF-4形成最稳定的阴离子,这与Cs+离子束轰击KPF6实验中,PF-6与PF-4的产额最高的结论一致.
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