摘要
采用密度泛函理论B3LYP/6—311+G^6方法,计算研究了(Me2BN3)n(n=1~3)簇合物的结构和性质.研究表明,环状多聚体(Me2BN3)n(n=1~3)的优化构型均为由不同子体系的叠氮基0-N和B原予相连形成的环状结构.讨论几何参数随聚合度的变化关系,同时对所有优化构型进行振动频率计算,对其IR谱进行归属,并与实验值进行了比较,结果发现计算值均可信.簇合物的热力学函数均随簇合物的聚合度n以及温度的增加而呈线性增加.由聚合反应的焓变可知,在298.2K下单体形成三聚体在热力学上是有利的,而形成二聚体则是不利的.
The (Me2BN3)n(n=1~3) clusters were optimized to obtain their structures and properties at the DFT- B3LYP/6-31 1 +G* level. The optimized clusters (MezBN3)n(n=2-3) all possess cyclic structure formed by B atoms bridged by the α-nitrogen of the azide groups. The relationships between geometrical parameters and oligomerization degree n are discussed. Their IR spectra are obtained and assigned by vibrational analysis and are reliable compared with the experimental results. The thermodynamic properties are linearly related with the oligomerization degree n as well as the temperature. Thermodynamic analysis of the gas-phase reaction shows that formation of the stable clusters (Me2BN3), is thermodynamically favorable by the enthalpies for n = 3, but unfavorable in the case of n = 2 at 298.2 K.
出处
《临沂师范学院学报》
2010年第3期90-95,共6页
Journal of Linyi Teachers' College
基金
中国博士后科学基金项目(20070410335)
江苏省博士后基金项目(0701024C)
山东省高等学校优秀骨干教师国际合作培养项目资助