簇合物(I_2InN_3)_n(n=1～4)的结构和稳定性的理论研究(英文)

Theoreticalstudy on the structure and stability of(I_2InN_3)_n(n=1～4) clusters

为寻求单一源前驱体,采用密度泛函理论DFT-B3LYP方法系统研究新的第IIIA主族叠氮簇合物的结构与性质关系.结果表明,簇合物(I2InN3)n(n=2～4)的优化构型均为由不同子体系的叠氮基α-N和In原子相连形成的环状结构,叠氮基以直线型存在.研究了几何参数随聚合度的变化趋势,并对计算获得的IR谱进行归属.能量和聚合焓均揭示簇合物的稳定性次序为3A>3B和4B>4C>4A>4D.簇合物(I2InN3)n(n=1～4)的热力学函数随温度升高和聚合度n增大而増加.热力学分析表明聚合反应在温度高达500K均可自发进行.

This study aims to design novel group Ilia azide clusters as single source precursors （SSP） hy exploiting systematic structure - property relationships at DFT-B3LYP level. The optimized （I2InN3）. （n=2-4） clusters all possess cyclic structure formed by In atoms bridged by the α-nitrogen of the azido groups, and azido in azides has linear structure. Structural changes with the oligomerization degree n were discussed and the calculated IR spectra were assigned. The computed total energies and enthalpies of oligomerization consistently indicate the stability ： 3A〉3B, and 4B〉 4C〉4A〉4D. Thermodynamic properties for （I2InN3）.（n=1-4） clusters increase with the oligomerization degree n and the tempera- ture increasing. Meanwhile, the oligomerizations can occur spontaneously at temperature up to 500 K.