Racine Julien, Touadjine Mohamed Abdelhak, Rahmouni Ali, Humbel Stéphane
Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
Université Tahar Moulay de Saida, Laboratoire de Modélisation et de Méthodes de Calcul, BP 138 cité ENNASR, 20000, Saida, Algérie.
J Mol Model. 2017 Jan;23(1):22. doi: 10.1007/s00894-016-3191-x. Epub 2017 Jan 7.
The A ground and the first B excited states of the methylenecyclopropene (triafulvene) are described by localized wave functions, based on 20 structures valence bond structures. The results are compared to CASSCF(4,4) calculations for both the energetics and the dipole moment. Additional calculations with partial electronic delocalization are presented, and it is shown that the dipole moment modification does not correspond to a situation where the antiaromatic situation prevails (with 4n electrons in the cycle). Part of the analysis uses a "trust factor" that helps to decide if a wave function is appropriate to describe a given state. The trust factor compares the VB wave function to the CASSCF's with their overlap. Finally, the valence bond density is used to produce density maps that illustrate the electron transfer upon excitation. Graphical Abstract A projector-based method compares CASSCF wave functions to local wave functions, including Lewis structures as shown in the picture. A "trust factor" (τ) is obtained. Both the ground state and the first excited state of the methylenecyclopropene are discussed.
基于20种价键结构的定域波函数描述了亚甲基环丙烯（三亚甲富烯）的A基态和首个B激发态。将结果与CASSCF(4,4)对能量和偶极矩的计算进行了比较。给出了具有部分电子离域的额外计算，结果表明偶极矩的改变并不对应于反芳香情况占主导（环中有4n个电子）的情形。部分分析使用了一个“信任因子”，它有助于判断一个波函数是否适合描述给定的状态。信任因子将VB波函数与其重叠的CASSCF波函数进行比较。最后，价键密度用于生成密度图，以说明激发时的电子转移。图形摘要：一种基于投影的方法将CASSCF波函数与定域波函数进行比较，包括如图所示的路易斯结构。得到了一个“信任因子”(τ)。讨论了亚甲基环丙烯的基态和首个激发态。
