摘要
在DFT-B3LYP/SDD水平上计算研究了第A族金属叠氮多聚体(Me2MN3)n(n=1～3,M=Ga,Al)的结构和性质.多聚体(Me2MN3)2,3的各优化构型均为环状,通过一子体系叠氮基的α-N和另一子体系的金属Ga或Al相连.二聚体(Me2MN3)2中含M2N2平面四元环结构,三聚体(Me2MN3)3具有结合能相近的扭船式和椅式两种构象,均含M3N3六元环结构.与单体相比,多聚体的几何参数变化较大.报道了它们在不同温度下的热力学性质,发现叠氮二甲基镓和铝体系以二聚体形式存在.
The DFT/B3LYP method with SDD basis set was used to study the structures and properties of the group ⅢA metallic azide clusters(Me_2MN_3)_n(n=1_3; M=Ga, Al). (Me_2MN_3)_(2,3) clusters all possess cyclic-like structures formed by Ga or Al atoms bridged by the α-nitrogen of the azide groups. (Me_2MN_3)_2 was found to exhibit the planar M_2N_2 ring structure.(Me_2MN_3)_3 involving a six-membered M_3N_3 ring was found to exhibit boat-twisting and chair-like structures with very similar binding energies. Compared to the monomer, the structural changes for the clusters are large. Thermodynamic properties of the monomer and its clusters at different temperatures were discussed, which reveals that the dimethylmetallic azide clusters of aluminium and gallium consist of the dimer.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2005年第5期922-926,F008,共6页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:20173028)资助.
