Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, 1428 Buenos Aires, Argentina.
Phys Chem Chem Phys. 2013 Jun 28;15(24):9594-604. doi: 10.1039/c3cp50736j. Epub 2013 May 13.
This work deals with the Fukui and dual reactivity descriptors within the framework of the spin-polarized density functional theory. The first and second derivatives of the electron density and the spin density with respect to the total number of electrons N = Nα + Nβ and with respect to the spin number NS = Nα-Nβ have been formulated by means of reduced density matrices in the representation of the spin-orbitals of a given basis set, providing the matrix extension of those descriptors. The analysis of the eigenvalues and eigenvectors of the Fukui and dual-descriptor matrices yields information on the role played by the molecular orbitals in charge-transfer and spin-polarization processes. This matrix formulation enables determining similarity indices which allows one to evaluate quantitatively the quality of the simple frontier molecular orbital model in conceptual density functional theory. Selected closed- and open-shell systems in different spin symmetries have been studied with this matrix formalism at several levels of electronic correlation. The results confirm the suitability of this approach.
这项工作涉及到基于自旋极化密度泛函理论的福井和双重反应性描述符。电子密度和自旋密度对总电子数 N=Nα+Nβ和自旋数 NS=Nα-Nβ的一阶和二阶导数，通过给定基组的自旋轨道的约化密度矩阵来表示，提供了这些描述符的矩阵扩展。福井和双描述符矩阵的特征值和特征向量的分析提供了分子轨道在电荷转移和自旋极化过程中所起作用的信息。这种矩阵表示形式可以确定相似性指数，从而可以定量评估简单前沿分子轨道模型在概念密度泛函理论中的质量。使用这种矩阵形式，在不同自旋对称性的不同电子相关水平下研究了几个闭壳层和开壳层系统。结果证实了这种方法的适用性。
