Geometrical optimization for strictly localized structures
Geometrical optimization for strictly localized structures
复制标题
DOI：
10.1063/1.1580094
复制
发表时间：
2003-07
影响因子：
4.4
通讯作者：
Y. Mo
中科院分区：
文献类型：
--
作者：
Y. Mo
最近我们提出了块定域波函数（BLW）方法，该方法综合了价键理论和分子轨道理论的优点，在假设所有电子和轨道都被划分为几个子群的基础上定义了共振结构的波函数。在这项工作中，我们实现了几何优化的BLW方法的基础上提出的算法Gianinetti和同事。因此，我们不仅可以研究共轭效应对分子稳定性的影响，还可以研究共轭效应对分子几何结构的影响。利用这一能力，在6- 31 G（d）和6-311+G（d，p）基组下，通过优化反式多烯C2 nH 2n +2（n=2-5）和甲酰胺及其类似物的离域和严格定域形式，研究了它们的π共轭效应.虽然人们已经很好地假定了π共振缩短单键，延长双键与π电子的离域跨越整个线在多烯，我们的严格定域结构的优化。
Recently we proposed the block localized wavefunction (BLW) approach which takes the advantages of valence bond theory and molecular orbital theory and defines the wavefunctions for resonance structures based on the assumption that all electrons and orbitals are partitioned into a few subgroups. In this work, we implement the geometrical optimization of the BLW method based on the algorithm proposed by Gianinetti and coworkers. Thus, we can study the conjugation effect on not only the molecular stability, but also the molecular geometry. With this capability, the π conjugation effect in trans-polyenes C2nH2n+2 (n=2–5) as well as in formamide and its analogs are studied by optimizing their delocalized and strictly localized forms with the 6-31G(d) and 6-311+G(d,p) basis sets. Although it has been well presumed that the π resonance shortens the single bonds and lengthens the double bonds with the delocalization of π electrons across the whole line in polyenes, our optimization of the strictly localized stru...