吡咯两类加聚物的密度泛函计算及结构与热化学性质关系  

Density functional theory studies of structure and thermochemical properties of two kinds of pyrrole polymers

作　　者：高进伟[1] 王学业[1] 李小兵[1] 禹新良[1] 

机构地区：[1]湘潭大学化学学院,湖南湘潭411105

出　　处：《计算机与应用化学》2006年第7期655-658,共4页Computers and Applied Chemistry

基　　金：湖南省教育厅重点资助项目(05A002)

摘　　要：采用B3LYP/6-31G~*方法对吡咯分子的两类加聚物体系(C_4H_4N)_n(n=1～4)进行了全优化计算,频率分析可知构型皆为稳定构型,在优化构型上计算了这两种加聚物总能量(E_T),零点能(ZPE),热容(C_p^0)和熵(S°),分析了两类加聚物的几何结构和成键特征,通过线性拟合得到了吡咯加聚物的热力学性质与聚合度n的关系,并计算了两类加聚物的反应焓变。计算表明吡咯加聚物具有稳定的链式构象,其中交错式加聚物具有更稳定的结构,吡咯加聚反应主要为交错加聚过程,可为同类化合物结构与性能关系的研究以及加成聚合反应机理研究提供方法和理论依据。Two kinds of pyrrole polymers （C4H4N）n（n = 1～4） were optimized by B3LYP/6-31G^＊. The vibration frequencies, total energy, zero point energy, capacity and entropy were calculated based on the optimized structures. The equilibrium structures and possibility of linkage were investigated by analyzing two kinds of pyrrole polymers （C4H4N）n（n = 1～4） geometric structures and vibrational frequency. The relationships between ET, ZPE, C^0p, S° and n were obtained by means of linear fitting. The formation enthalpy （△Hn） of two kinds of pyrrole polymers （C4H4N）n（n = 1～4） was calculated. The calculated results indicate that the two catenarian structures of pyrrole polymers are of stable, and staggered one is of the better stability. The values of ET, ZPE, C0^p and S° change with n regularly, all the correlation coefficients are over 0.998. The main polymerization style of pyrrole polymers is the staggered polymerized process.

关 键 词：吡咯 加聚物 密度泛函理论 热化学性质 

分 类 号：O6-04[理学—化学] O631