Abstract: P₂+P₄(T_d)+P₈(C_2v)→P₁₄(C_s)(A),P₈(C_2v)+3P₂→P₁₄(C_2v)(Ⅰ)(B),P₁₀(C_2v)+2P₂→P₁₄(C_2v)(Ⅱ)(C)are designed by acting P₂,P₄ (T_d),P₈(C_2v)and P₁₀(C_2v)as the structural units, Using Gaussian-94 ab initio program, the four kinds of structural units and three configurations of P₁₄ cluster[C_s,C_2v(Ⅰ),C_2v(Ⅱ)] are performed by full geometric optimization by choosing₆-31Gbasis set.The calculated results of relative energy show that the configurations of P₁₄(C_s) and P₁₄(C_2v)(Ⅰ)are stable,Furthermore, we design(7/2)P₄(T_d)→P₁₄(D),7P₂→P₁₄(E), the relative energy shows that the structure of P₁₄ (C_s)is stable, The results of the three structures of the P₁₄ cluster show that the range of single bond lengths which link phosphorous atom is 0.220~0.228 nm,the range of double bond lengths is 0.200~0.202 nm, which are in accordance with the experimental values.

Key words: P₁₄ cluster, Structural unit, Geometric configuration