Departament de Química Física, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
J Comput Chem. 2013 Jun 5;34(15):1321-31. doi: 10.1002/jcc.23257. Epub 2013 Feb 22.
We introduce a pseudosymmetry analysis of molecular orbitals by means of the newly proposed irreducible representation measures. To do that we define first what we consider as molecular pseudosymmetry and the relationships of this concept with those of approximate symmetry and quasisymmetry. We develop a general algorithm to quantify the pseudosymmetry content of a given object within the framework of the finite group algebra. The obtained mathematical expressions are able to decompose molecular orbitals by means of the irreducible representations of any reference symmetry point group. The implementation and usefulness of the pseudosymmetry analysis of molecular orbitals is demonstrated in the study of σ and π orbitals in planar and nonplanar polycyclic aromatic hydrocarbons and the t2 g and eg character of the d-orbitals in the FeH6 anion in its high spin state along the Bailar twist pathway.
我们通过新提出的不可约表示测度，介绍了分子轨道的赝对称分析。为此，我们首先定义了什么是分子赝对称，以及这个概念与近似对称和准对称的关系。我们开发了一种通用算法，用于在有限群代数框架内量化给定对象的赝对称含量。所得到的数学表达式能够通过任何参考对称点群的不可约表示来分解分子轨道。分子轨道赝对称分析的实现和有效性在平面和非平面多环芳烃的σ和π轨道以及高自旋状态下FeH6阴离子的 d 轨道的 t2g 和 eg 特征沿 Bailar 扭曲途径的研究中得到了证明。
