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以Ｐ_２、Ｐ_４（Ｔｄ）、Ｐ_８（Ｃ_（２ｖ））及Ｐ_（１０）（Ｃ_（２ｖ））为结构单元设计了Ｐ_２＋Ｐ_４（Ｔ_ｄ）＋Ｐ_８（Ｃ_（２ｖ））→Ｐ_（１４）（Ｃ_ｓ）（Ａ）、Ｐｓ（Ｃ_（２ｖ）＋３Ｐ_２→Ｐ_（１４）（Ｃ_（２ｖ））（Ｉ）（Ｂ）、Ｐ_（１０）（Ｃ_（２ｖ）＋２Ｐ_２→Ｐ１４（Ｃ_（２ｖ））（Ⅱ）（Ｃ），利用从头算Ｇａｕｓｓｉａｎ－９４程序，选择６－３１Ｇ基组，对４种结构单元及Ｐ_（１４）原子簇的３种几何构型Ｃｓ、Ｃ_（２ｖ）（Ⅰ）、Ｃ_（２ｖ）（Ⅱ）进行全优化。相对能量的计算结果表明，Ｐ_（１４）（Ｃ_ｓ）与Ｐ_（１４）（Ｃ_（２ｖ））（Ⅰ）构型稳定。进一步设计（７／２）Ｐ_４（Ｔ_ｄ）→Ｐ_（１４）（Ｄ）及７Ｐ_２→Ｐ_（１４）（Ｅ），其相对能量表明，Ｐ_（１４）（Ｃ_ｓ）构型是稳定的．磷与磷连结单键键长范围为０．２２０～０．２２８ｎｍ，双键键长范围为０．２００～０．２０２ｎｍ，与实验结果大体相当。
P_2 + P_4 (T_d) + P_8 (C_ (2v)) → P_ (14) (C_s) were designed with P_2, P_4 (Td), P_8 (C_2v) and P_ (10) (A) and Ps (C 2v + 3P 2 → P 14 (C 2v) (I) (B) and P 10 (C 2v + 2P 2 → P 14 C 2v) (C). The geometrical configurations of Cs, C 2v, I and C 2v of three kinds of structural units and P 14 clusters were selected by using ab initio Gaussian-94 program and 6-31G basis set. The results of relative energy calculation show that the configurations of P_ (14) (C_s) and P_ (14) (C_ (2v)) (Ⅰ) are stable.The design of (7/2) P_4 ) → P_ (14) (D) and 7P_2 → P_ (14) (E). The relative energies show that the P_ (14) (C_s) Phosphorus and phosphorus coupling single bond length in the range of 0.220 ~ 0.228nm, a double bond length in the range of 0.200 ~ 0.202nm, roughly with the experimental results.