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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Synchrotron charge-density studies in materials chemistry: 16 K X-ray charge density of a new magnetic metal-organic framework material, [Mn2(C8H4O4)2(C3H7NO)2].
TL;DR: A new magnetic metal-organic framework material, [Mn(2)(C(8)OH(4)(4))(2)C(3)H(7)NO)(2)], has been synthesized, which consists of chains of carboxylate-bridged Mn atoms interconnected with acid linkers, giving much larger interchain than intrachain Mn...Mn distances.
Journal ArticleDOI
Donor-Acceptor Complexes between 1,2,5-Chalcogenadiazoles (Te, Se, S) and the Pseudohalides CN- and XCN- (X=O, S, Se, Te).
Nikolay A. Semenov,Dmitry E. Gorbunov,Dmitry E. Gorbunov,Margarita V. Shakhova,Margarita V. Shakhova,G. E. Sal’nikov,G. E. Sal’nikov,Irina Yu. Bagryanskaya,V.V. Korolev,Jens Beckmann,Nina P. Gritsan,Nina P. Gritsan,Andrey V. Zibarev,Andrey V. Zibarev,Andrey V. Zibarev +14 more
TL;DR: Donor-acceptor (D-A) complexes between 3,4-dicyano-1,2,5-chalcogenadiazoles and the pseudohalides CN- and XCN- were studied experimentally and theoretically and characterized by X-ray diffraction, UV/Vis and NMR spectroscopy, and DFT and QTAIM calculations.
Journal ArticleDOI
Halogen bonding. the role of the polarizability of the electron-pair donor
TL;DR: A detailed analysis of the MEPs reveals that considering only the static electrostatic interactions is not sufficient to explain the nature of these interactions, and the electrostatic forces and charge transfer play an important role not only in the stabilization of the complex, but also in the determination of the molecular geometry of equilibrium.
Journal ArticleDOI
Theoretical Insights into the Selective Extraction of Americium(III) over Europium(III) with Dithioamide-Based Ligands.
Cui Wang,Cui Wang,Qun-Yan Wu,Xiang-He Kong,Xiang-He Kong,Cong-Zhi Wang,Jian-Hui Lan,Chang-Ming Nie,Zhifang Chai,Wei-Qun Shi +9 more
TL;DR: Three dithioamide-based ligands are investigated and their extraction behaviors with Am(III) and Eu( III) ions using the scalar-relativistic density functional theory and it is suggested that the Am-S/N bonds possess more covalency compared to the Eu-S-N bonds, and the M-S bonds haveMore covalent character than the M -N bonds.
Journal ArticleDOI
Role of dG/dw and dV/dw in AIM analysis: an approach to the nature of weak to strong interactions.
Waro Nakanishi,Satoko Hayashi +1 more
TL;DR: Relations between AIM functions, such as dV(b)(r(c))/dw, dG(b)*(r( c)/)/dW, dH(b)(r)(c) /d, and d(2)H( b)(r-c)/d[H(B)(r)c)) - V(b(r (c)))/2], are discussed, which help to understand the nature of interactions.
References
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