叠氮二乙基铝和镓多聚体结构和性质的密度泛函理论研究(英文)  

Structure-properties of Diethylmetallic Azides Clusters of Aluminum and Gallium by DFT

作　　者：夏其英[1,2] 马登学[2] 杨吉民[1] 

机构地区：[1]临沂师范学院化学化工学院,山东临沂276005 [2]南京理工大学化工学院,江苏南京210094

出　　处：《含能材料》2009年第3期260-264,共5页Chinese Journal of Energetic Materials

基　　金：China Postdoctoral Science Foundation(No.20070410335);Jiangsu Postdoctoral Research Funds(No.0701024C);the Foundation from Linyi Normal University

摘　　要：采用DFT-B3LYP/SDD方法系统研究了(Et2MN3)n(n=1 -3,M=Al, Ga)体系。二聚体(Et2MN3)2和三聚体(Et2MN3)3(M=Al, Ga)分别拥有四元环M2N2和六元环M3N3结构。与单体相比,二聚体(Et2MN3)2和三聚体(Et2MN3)3(M=Al, Ga)的键长变化次序均为Nα—M>Nα—Nβ>Nβ—Nγ≈M—C。二聚体(Et2AlN3)2的结合能比(Et2GaN3)2低35.44 kJ.mol-1,而三聚体(Et2AlN3)3的结合能比(Et2GaN3)3低45.61 kJ.mol-1。热力学性质表明叠氮二乙基铝和镓体系在298.2 K温度下均以二聚体为主。在低于500 K的温度下,二聚化和三聚化反应在热力学上是有利的。（Et2MN3 ）.（n = 1 to 3, M = Al, Ga） clusters were studied by DFT/B3LYP method with SDD basis set. The dimer（ Et2MN3 ）2 and trimer（ Et2MN3 ）3 （ M = Al, Ga） are found to exhibit four-membered M2N2 and six-membered M3N3 ring structure, respectively. Compared with the monomer, the order of the bond length changes for the dimer （Et2MN3）., and trimer（Et2MN3）3（M =Al, Ga） is as follows：Nα-M〉Nα-Nβ〉Nβ-Nγ≈M-C. Binding energies of the dimer （ Et2AlN3 ）2 and trimer（Et2AlN3 ） 3 clusters are 35.44 and 45.61 kJ·mol ^-1 lower than that of （Et2 GaN3 ）2 and （Et2GaN3）3 clusters, respectively. Thermodynamic properties show that the dimer is the main composition of the （ Et2MN3 ）, （ n = 1 to 3, M = Al, Ga） clusters at 298.2 K. The dimerization and trimerization are very favorable thermodynamically below 500K.

关 键 词：物理化学 (Et2MN3)n(n=1-3 M=Al Ga) 密度泛函理论(DFT) 结合能 热力学性质 

分 类 号：O631.1[理学—高分子化学]