Structure and Electronic Properties of ZH3, ZH+4 and ZH4X (Z=N, P, As, Sb, Bi, X=F, Cl, Br, I)*
LI Zhi-Feng1**, LEI Zhi-Min1, YANG Xiao-Ping2
1.College of Chemical Engineering and Technology, Tianshui Normal University, Tianshui 741001, China;
2.School of Civil Engineering, Tianshui Normal University, Tianshui 741001, China
Abstract The structure and electronic properties of ZH3, ZH+4 and ZH4X (Z=N, P, As, Sb, Bi, X=F, Cl, Br, I) are investigated by MP2/def2-TZVP method. The results show that with the increase of the atomic number of the nitrogen group element, the s component in the center atomic hybrid orbital of its hydride (ZH3) decreases, while the p component increases gradually, and the degree of the hybridized orbital deviating from the plane increases successively, resulting in the most “plane” of NH3 spatial configuration and the most “cone” of BiH3. Although the lone pair electrons provided by an unequal sp3 hybridized orbital of Z in ZH3 are formed with H+in cationic ZH+4, four H—Z bonds are equivalent in ZH+4, and Z presents an isotropic sp3 hybridization. ZH4X is a tetrahedral structure with C3v symmetry, and the compound driving force between ZH3 and HX comes from the ionic hydrogen bond (H3Z…H*—X) rather than the electrostatic interaction between ZH+4 and X- (ZH+4X-). The main driving force of the molecule is the electron transfer from LP1(Z) to σ*(H*—X).
LI Zhi-Feng, LEI Zhi-Min, YANG Xiao-Ping. Structure and Electronic Properties of ZH3, ZH+4 and ZH4X (Z=N, P, As, Sb, Bi, X=F, Cl, Br, I)*[J]. Chinese Journal of Chemical Education, 2020, 41(8): 18-23.