Electron pairing and chemical bonds: Bonding in hypervalent molecules from analysis of Fermi holes

Abstract

ABSTRACT:Bonding in the hypervalent molecules SF , BrF , PF , and SF was belonging to type II. The eigenvalues and eigenvectors of type I molecules distinguished between classic two-center two-electron bonds and three-center four-electron bonds, whereas the results of diagonalization for type II molecules demonstrated the presence of substantial reorganization of the valence state of the central atom leading to equivalent bonds and the highest expected symmetry of the molecule. ᮊ

On the Electronic Structure ofmer,trans‐[RuCl3(1H‐indazole)2(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

“…[98][99][100][101][102][103] Its principles are described in the original literature. [39][40][41] Especially interesting and chemically relevant information can be extracted from the holes defined by atomic domains resulting from Bader or Mulliken analysis, but more complex domains, formed by the union of several atomic domains, which correspond, for example, to certain functional groups or interesting molecular fragments, can be analyzed as well. In any case, the holes provide information about the electron pairs (chemical bonds, core and valence lone pairs) retained in the domain and about the broken or dangling valences resulting from the formal splitting of the bonds required for the isolation of the corresponding fragments from the rest of the molecule.…”

“…XANES and EXAFS experiments were performed to elucidate the physical oxidation state of the central metal in 1. The localized orbitals (1-3) and DAFH analysis [39][40][41] (1) were used to further elucidate the electron structure of the {Ru(NO)} 6 fragment in 1. QTAIM [42,43] and Mulliken population analyses (MPA) were performed to gain insight into the nature of the coordination bonds.…”

Electron pairing and chemical bonds: Pair localization in ELF domains from the analysis of domain averaged Fermi holes

“…Domain averaged Fermi holes, introduced some time ago [25][26][27] as a generalization of the original concept by Wigner and Seitz, 28 have proved to represent a new and efficient tool for the interpretation of the nature of chemical bond, and numerous recent applications of this new methodology has clearly shown its usefulness for the elucidation of the picture of bonding, especially in molecules with nontrivial bonding pattern. [29][30][31][32][33][34] The domain-averaged Fermi holes can most straightforwardly be introduced by eq.…”

Domain-averaged Fermi holes - a new means of visualization of chemical bonds. Bonding in hypervalent molecules

“…Since, however, this approach was originally applied only at the level of the simple semiempirical AM1 method [29] which certainly does not meet the contemporary computational standards, we report in this study the extension of this approach to the level of ab initio SCF methods. The primary aim of this study is to analyze how the picture of bonding changes in response to the systematic variation of the basis set from the minimal STO-3G to the rather exible 6-31G** basis.…”