Journal Article10.1063/1.1501133
From weak to strong interactions: A comprehensive analysis of the topological and energetic properties of the electron density distribution involving X–H⋯F–Y systems
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TL;DR: In this paper, the topological and energetic properties of the electron density distribution ρ(r) of isolated pairwise H⋯F interaction have been theoretically calculated at several geometries and represented against the corresponding internuclear distances.
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Abstract: The topological and energetic properties of the electron density distribution ρ(r) of the isolated pairwise H⋯F interaction have been theoretically calculated at several geometries (0.8<d<2.5 A) and represented against the corresponding internuclear distances. From long to short geometries, the results presented here lead to three characteristic regions, which correspond to three different interaction states. While the extreme regions are associated to pure closed-shell (CS) and shared-shell (SS) interactions, the middle one has been related to the redistribution of ρ(r) between those electronic states. The analysis carried out with this system has permitted to associate the transit region between pure CS and SS interactions to internuclear geometries involved in the building of the H–F bonding molecular orbital. A comparative analysis between the formation of this orbital and the behavior of some characteristic ρ(r) properties has indicated their intrinsic correspondence, leading to the definition of a bond degree parameter [BD=HCP/ρCP; HCP and ρCP being the total electron energy density and the electron density value at the H⋯F (3,−1) critical point]. Along with the isolated pairwise H⋯F interaction, 79 X–H⋯F–Y (neutral, positively and negatively charged) complexes have been also theoretically considered and analyzed in terms of relevant topological and energetic properties of ρ(r) found at their H⋯F critical points. In particular, the interaction energies of X–H⋯F–Y pure CS interactions have been estimated by using the bond degree parameter. On the other hand, the [F⋯H⋯F]− proton transfer geometry has been related to the local maximum of the electron kinetic energy density (GCP)max.
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References
Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities
TL;DR: In this article, the topological properties of ρ(r) at the intermolecular critical points of 83 experimentally observed hydrogen bonds [X-H⋯O (X=C,N,O)], using accurate X-ray diffraction experiments, were analyzed.
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Characterization of c-h-o hydrogen-bonds on the basis of the charge-density
Uwe Koch,Paul L. A. Popelier +1 more
TL;DR: In this paper, a set of criteria are proposed based on the theory of "atoms in molecules" to establish hydrogen bonding, even for multiple interactions involving C-H-O hydrogen bonds.
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A Bond Path: A Universal Indicator of Bonded Interactions
TL;DR: In this paper, the Ehrenfest force acting on an element of ρ(r) and the virial field that determines its potential energy are obtained from equations of motion for the electronic momentum and virial operators, respectively.
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Calculation of the average properties of atoms in molecules. II
TL;DR: In this paper, an algorithm for the calculation of the average properties of an atom in a molecule is described. But this algorithm is restricted to the case where the atom is defined within the topological theory of molecular structure, a theory which defines atoms, bonds, structure and structural stability in terms of a system's charge distribution.
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About the evaluation of the local kinetic, potential and total energy densities in closed-shell interactions
TL;DR: In this paper, the local kinetic G( r ), potential V( r ), and total energy densities, calculated at the critical points of 37 H⋯F closed-shell interactions by quantum mechanical methods, have been compared to their estimated values obtained by using an approximate evaluation of G(r ) and the local form of the virial theorem.
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