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.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
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
