[1]夏其英.(X2InN3)_n(n=1-3;X=F,Cl,Br,I)簇合物的密度泛函理论研究[J].南京理工大学学报(自然科学版),2010,(02):207-212.
 XIA Qi-ying,MA Deng-xue.Studies on Clusters (X2InN3)n(n=1-3;X=F,Cl,Br,I) with Density Functional Theory[J].Journal of Nanjing University of Science and Technology,2010,(02):207-212.
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(X2InN3)_n(n=1-3;X=F,Cl,Br,I)簇合物的密度泛函理论研究
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《南京理工大学学报》(自然科学版)[ISSN:1005-9830/CN:32-1397/N]

卷:
期数:
2010年02期
页码:
207-212
栏目:
出版日期:
2010-04-30

文章信息/Info

Title:
Studies on Clusters (X2InN3)n(n=1-3;X=F,Cl,Br,I) with Density Functional Theory
作者:
夏其英1 2 马登学1
1. 南京理工大学化工学院, 江苏南京210094; 2. 临沂师范学院化学化工学院, 山东临沂276005)
Author(s):
XIA Qi-ying 12MA Deng-xue1
1.School of Chemical Engineering,NUST,Nanjing 210094,China;2.School of Chemistry and Chemical Engineering,Linyi Normal University,Linyi 276005,China
关键词:
簇合物 密度泛函理论 几何构型 电子结构 取代基效应 热力学性质
Keywords:
clusters density functional theory geometric configurations electronic structures effect of substituents thermodynamic properties
分类号:
O641.1
摘要:
采用密度泛函理论B3LYP/Lanl2dz方法,计算研究了(X2InN3)n(n=1-3;X=F,Cl,Br,I)簇合物的几何构型、电子结构和聚合反应热力学性质,讨论了取代基效应。研究表明,二聚体(X2InN3)2和三聚体(X2InN3)3(X=F,Cl,Br,I)的优化几何构型均为由不同子体系的叠氮基α-N和In原子相连而成的环状结构。在卤原子(X)取代簇合物中,取代位附近的键长、键角和原子电荷改变较大。由前线轨道能隙ΔEgap和反应焓变ΔH0可见,同类簇合物的稳定性排序为(F2InN3)n>(Cl2InN3)n>(Br2InN3)n>(I2InN3)n(n=1-3)。求得298.2 K温度下聚合反应的吉布斯自由能变化ΔG0均为负值,表明反应可自发进行。此外,还发现簇合物的性质随聚合度n增加的变化规律。
Abstract:
The geometric configurations,electronic structures and thermodynamic properties of polymerizations are studied at the B3LYP/Lanl2dz level of density functional theory(DFT).The effect of substituents on the above properties is discussed.The calculated results show that the optimized dimer(X2InN3)2 and trimer(X2InN3)3(X=F,Cl,Br,I) all possess cyclic structure formed by In atoms bridged by the α-nitrogen of the azide groups.Halogen X substitution largely affects the bond lengths,bond angles,and charge distributions on the atoms near the substitution positions.From the calculation of the energy gap ΔEgap and the oligomerization enthalpies ΔH0,it is indicated that the stability order is as follows:(F2InN3)n>(Cl2InN3)n>(Br2InN3)n>(I2InN3)n(n=1-3).The Gibbs energies ΔG0 of the oligomerizations at 298.2 K are negative,which indicates the oligomerization can occur spontaneously.The change rule of the properties of the clusters with the increase of the oligomerization degree n is discovered.

参考文献/References:

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备注/Memo

备注/Memo:
基金项目: 中国博士后科学基金( 20070410335); 江苏省博士后基金( 0701024C ); 临沂师范学院科研基金项目 ( XJB04004) ; 山东省高等学校优秀骨干教师国际合作培养项目 ?? 作者简介: 夏其英( 1974- ) , 女, 博士, 副教授, 主要研究方向: 计算化学, E-mail: x iaq iy ing@ 163. com。
更新日期/Last Update: 2010-04-30