SnAl4-和PbAl4-：新型平面四配位分子  

SnAl_4^- and PbAl_4^-: Two New Planar Tetra-coordinate Molecule

作　　者：高斯萌[1] 贺海鹏[1] 丁益宏[1] 

机构地区：[1]吉林大学理论化学研究所,理论化学计算国家重点实验室,长春130021

出　　处：《高等学校化学学报》2013年第1期185-191,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21073074,20773054);新世纪优秀人才支持计划资助

摘　　要：通过全局结构搜索,在CCSD(T)/aug-cc-pVTZ&CEP-121G//B3LYP/6-311+G(d)&LANL2DZ水平上(其中CEP-121G和LANL2DZ用于Sn和Pb原子),构建了XAl-4(X=Sn,Pb)的异构化势能面,对于X=Si,Ge体系,平面四配位X异构体明显是体系的全局极小,但对于X=Sn,Pb而言,除了平面四配位X异构体外,还存在一个几乎与其等能量但未被关注的金字塔形结构.此外,从X=Si和Ge到X=Sn和Pb,体系势能面变得更为平滑.本文不但进一步检验了平面化学中的17价电子规则,也阐明了中心原子的取代效应对平面四配位结构稳定性的重要影响.The isomerization potential energy surface of XAI4- （X = Sn, Pb ） at the CCSD （T）/aug-cc- pVTZ＆CEP-121G//B3LYP/6-311 ＋G（d） ＆LANL2DZ level（ CEP-121G and LANL2DZ for Sn, Pb only） was constructed by means of the global isomeric search method. The results show that for X = Si/Ge, the planar tetra-coordinate X structure is the global isomer. Yet, for X=Sn/Pb, in addition to the planar tetra-coordinate X isomer, a ＂pyramidal＂ structure lies almost isoenergetic. Morevoer, from X = Si/Ge to X = Sn/Pb, the po- tential energy surface becomes smoother. The present work not only provides new clues to the 17 valence elec- tron rule in the planar chemistry, but demonstrates that the doping at the X-site would have significant influ- ence on the stability of the planar tetra-coordinate structure.

关 键 词：平面四配位 势能面 SnAl4-体系 PbAl4-体系 理论研究 

分 类 号：O641[理学—物理化学]