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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Journal ArticleDOI
Intermolecular interactions-photophysical properties relationships in phenanthrene-9,10-dicarbonitrile assemblies
Anastasiia Afanasenko,Anastasiia Afanasenko,Alexander S. Novikov,Tatiana G. Chulkova,Yakov M. Grigoriev,Ilya E. Kolesnikov,Stanislav I. Selivanov,Galina L. Starova,Andrey A. Zolotarev,Anatoly N. Vereshchagin,Michail N. Elinson +10 more
TL;DR: In this article, the X-ray structures of phenanthrene-9,10-dicarbonitriles were studied at the M06−2X/6−311++G(d,p) level of theory and topological analysis of the electron density distribution within the framework of QTAIM method.
Journal ArticleDOI
Ab initio study of hydrogen adsorption on Zn2(NDC)2(diPyTz) metal-organic framework decorated with alkali and alkaline earth metal cations
Saeid Yeganegi,Vahid Sokhanvaran +1 more
TL;DR: In this paper, the effect of decorating the organic linker of Zn2(NDC)2(diPyTz) with alkali and alkaline earth metal cations (Li+, Na+, K+, Be2+, Mg2+) on hydrogen adsorption was studied.
Journal ArticleDOI
Charge density studies on [(NO)Fe(S2C6H4)2][PPN] and [(NO)3Fe(S2C6H4)3] complexes
TL;DR: In this paper, the charge density studies of chemical bonds for two iron complexes, [(NO)Fe(S,S-C 6 H 4 ) 2 ] [PPN] (1), where PPN = N(Pph 3 ) 2 and Fe 3 (NO) 3 (S,C 6H 4 ) 3 (2), were investigated in terms of the topological properties at bond critical points based on the ''atoms in molecule'' theory.
Journal ArticleDOI
Ab initio calculations on C6H6···(HF)n clusters X-H···π hydrogen bond
TL;DR: In this article, MP2/6-311++G(d,p) calculations on C6H6−·(HF)n clusters were performed and full optimizations were carried out for systems containing up to four HF molecules (n = 4).
Journal ArticleDOI
NMR Chemical Shift of a Helium Atom as a Probe for Electronic Structure of FH, F-, (FHF)-, and FH2.
TL;DR: It is shown that the Laplacian of helium chemical shift, ∇2δHe, is sensitive to fluorine atom lone pair localization regions, and it can be used for the visualization of the outer electronic shell, which could be used to evaluate the proton accepting ability.
References
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Journal ArticleDOI
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
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