The correlation theory of the chemical bond

Szalay, Szilárd and Barcza, Gergely and Szilvási, Tibor and Veis, Libor and Legeza, Örs (2017) The correlation theory of the chemical bond. SCIENTIFIC REPORTS, 7 (1). pp. 1-10. ISSN 2045-2322

Preview

Text s41598_017_02447_z_u.pdf Download (2MB) | Preview

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.

Actions (login required)

Edit Item