量子化学计算中基组效应对几何结构和性质影响的研究  

Studies on the effect of the basis sets on the geometrical structure and bonding properties in quantum chemistry calculation

作　　者：周宏伟[1] 周歌[1] 郑文旭[1] 田安民[1] 

机构地区：[1]四川大学化学学院,四川成都610064

出　　处：《化学研究与应用》2006年第9期1029-1034,共6页Chemical Research and Application

基　　金：国家自然科学基金(20373045)资助项目;教育部博士点基金(20020610024)资助项目

摘　　要：本文选择28个有代表性的化合物,在20种基组下进行量子化学计算,用Gaussian98(A.11)和AIM2000(V2.0)对它们进行研究。在分子成键性质的分析和判断中,使用AIM和NBO方法得到的结果比采用Mu llik-en集居分析方法更合理。通过系统化学计算表明,高级别的方法和基组是获得可靠的分子几何结构和性质的必要保证。采用6-31+G*以上的基组可以得到可信的分子几何结构。高级别的振动频率计算是确定分子稳定存在的一项必不可少的工作。b31yp/cc-pVDZ是一种经济的、各种体系下计算结果可靠的计算水平。在分子成键性质的分析和判断中,AIM和NBO方法可以给出合理可靠的结果。采用Mu lliken集居分析方法,可能会给出不可靠的结果。In this work,Gauasian 98（A. 11 ）and AIM2000（V2.0） were used to calculate the geometric structures and bonding properties of the 28 typical compounds at 20 kinds of basis sets. The studies showed that the results obtained from atom in molecule （AIM） analysis and from natural bond orbital（NBO） analysis were more reliable than those of Mulliken population analysis. Then the calculation results were used to estimate bonding properties of molecules. The calculation results showed that the high computa- tional level is necessary for obtaining the stable geometrical structures and the bonding properities. The computation of vibrational frequency at high level is also necessary for estimatinjg the stabilities of a molecule. The results are reliable using AIM and NBO analysis in estimating the bonding properties of a molecule,while the results by Mulliken population analysis may be tmstless.

关 键 词：成键性质 AIM NBO Mulliken集居数 

分 类 号：O614.12[理学—无机化学]