The correlation theory of the chemical bond

Abstract The quantum mechanical description of the chemical bond is generally given in terms of delocalized bonding orbitals, or, alternatively, in terms of correlations of occupations of localised orbitals. However, in the latter case, multiorbital correlations were treated only in terms of two-orb...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autores principales: Szilárd Szalay, Gergely Barcza, Tibor Szilvási, Libor Veis, Örs Legeza
Formato: article
Lenguaje:EN
Publicado: Nature Portfolio 2017
Materias:
R
Q
Acceso en línea:https://doaj.org/article/4129f7c11e3a4a54ab02131bb57134d3
Etiquetas: Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
Descripción
Sumario:Abstract The quantum mechanical description of the chemical bond is generally given in terms of delocalized bonding orbitals, or, alternatively, in terms of correlations of occupations of localised orbitals. However, in the latter case, multiorbital correlations were treated only in terms of two-orbital correlations, although the structure of multiorbital correlations is far richer; and, in the case of bonds established by more than two electrons, multiorbital correlations represent a more natural point of view. Here, for the first time, we introduce the true multiorbital correlation theory, consisting of a framework for handling the structure of multiorbital correlations, a toolbox of true multiorbital correlation measures, and the formulation of the multiorbital correlation clustering, together with an algorithm for obtaining that. These make it possible to characterise quantitatively, how well a bonding picture describes the chemical system. As proof of concept, we apply the theory for the investigation of the bond structures of several molecules. We show that the non-existence of well-defined multiorbital correlation clustering provides a reason for debated bonding picture.