Journal ArticleDOI
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
TLDR
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.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.read more
Citations
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9-Ethyladenine: Mechanochemical Synthesis, Characterization, and DFT Calculations of Novel Cocrystals and Salts
Yannick Roselló,Mónica Benito,Núria Bagués,Núria Martínez,Alba Moradell,Ignasi Mata,Judit Galcera,Miquel Barceló-Oliver,Antonio Frontera,Elies Molins +9 more
TL;DR: In this article, a liquid-assisted grinding and solvent crystallization of the modified nucleobase 9-ethyladenine with several carboxylic acids is described, and a new solid for the new solid is presented.
Journal ArticleDOI
Computational study of the process of hydrogen bond breaking: The case of the formamide–formic acid complex
TL;DR: It is shown that the spatial derivatives of ΔE, the topology of ρ(r), and qualitative changes noticed in U(r) = 0 isocontours allow to identify a precise distance R for which one can say the NH···O hydrogen bond has broken.
Journal ArticleDOI
Polybromides of pyridinium and quinolinium-type cations: Cation-induced structural diversity and theoretical analysis of Br⋯Br interactions
Igor D. Gorokh,Sergey A. Adonin,Alexander S. Novikov,Maxim N. Sokolov,Denis G. Samsonenko,Vladimir P. Fedin +5 more
TL;DR: In this article, four polybromide salts containing pyridinium type and quinolinium-type cations were isolated from HBr/Br2 solutions, and DFT calculations allowed estimation of Br⋯Br halogen bonding energies (0.9-7.5kcal/mol).
Journal ArticleDOI
Symmetrical Noncovalent Interactions Br···Br Observed in Crystal Structure of Exotic Primary Peroxide
TL;DR: The intermolecular noncovalent interactions Br···Br in the single-crystal XRD structure of the peroxo compound were studied theoretically using quantum chemical calculations and quantum theory of atoms in molecules analysis to suggest its stabilization in the solid state.
Journal ArticleDOI
Charge-density distribution in potassium dihydrogen phosphoglycolate--a comparison of phosphate and phosphonate groups.
TL;DR: Analysis of the experimental and theoretical charge-density distribution in potassium dihydrogen phosphoglycolate has been performed, finding that the coordination of potassium exerts a small effect on the phosphate group, whereas more pronounced changes may be observed concerning the ellipticities of the C-O bonds.
References
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Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
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