ZH3,ZH4+及ZH4X(Z=N,P,As,Sb,Bi,X=F,Cl,Br,I)的结构与电子性质  

Structure and Electronic Properties of ZH3,ZH+4 and ZH4X(Z=N,P,As,Sb,Bi,X=F,Cl,Br,I)

作　　者：李志锋 雷志敏 杨筱平 LI Zhi-Feng;LEI Zhi-Min;YANG Xiao-Ping(College of Chemical Engineering and Technology,Tianshui Normal University,Tianshui 741001,China;School of Civil Engineering,Tianshui Normal University,Tianshui 741001,China)

机构地区：[1]天水师范学院化学工程与技术学院,甘肃天水741001 [2]天水师范学院土木工程学院,甘肃天水741001

出　　处：《化学教育（中英文）》2020年第8期18-23,共6页Chinese Journal of Chemical Education

基　　金：国家自然科学基金(21463023);甘肃省自然科学基金(17JR5RE010);天水师范学院教学研究项目(SYJY2018B26)。

摘　　要：采用MP2/def2-TZVP理论方法考察了ZH3,ZH+4及ZH4X(Z=N,P,As,Sb,Bi,X=F,Cl,Br,I)的结构与电子性质。结果表明,随着氮族元素原子序数的递增,其氢化物(ZH3)中心原子杂化轨道中s成分减小,p成分逐渐增大,杂化轨道偏离平面的程度依次增大,导致NH3空间构型的最为"平面",而BiH3最为"锥形"。尽管阳离子ZH+4由ZH3中Z的一个不等性sp3杂化轨道提供孤对电子与H+形成,但ZH+4中4个Z-H键等价,Z总体呈现等性sp3杂化。ZH4X均为C3v对称的四面体结构,ZH3与HX之间的作用驱动力来源于离子型的氢键(H3Z…H*-X)而非ZH+4与X-阴阳离子对(ZH+4X-)间的静电作用,H3Z…H*-X内的电子转移主要发生在轨道LP1(Z)与σ*(H*-X)之间。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 C3 v 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)toσ*(H*-X).

关 键 词：氮族元素 卤族元素 结构 电子性质 

分 类 号：O611-4[理学—无机化学] G642[理学—化学]