info:eu-repo/semantics/article
Fukui and dual-descriptor matrices within the framework of spin-polarized density functional theory
Fecha
2013-04-19Registro en:
Alcoba, Diego Ricardo; Lain, Luis; Torre, Alicia; Oña, Ofelia Beatriz; Chamorro, Marcelo Eduardo; Fukui and dual-descriptor matrices within the framework of spin-polarized density functional theory; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 15; 24; 19-4-2013; 9594-9604
1463-9076
Autor
Alcoba, Diego Ricardo
Lain, Luis
Torre, Alicia
Oña, Ofelia Beatriz
Chamorro, Marcelo Eduardo
Resumen
This work deals with the Fukui and dual reactivity descriptors within the framework of the spinpolarized 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 = Na + Nb and with respect to the spin number NS = Na - Nb 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.