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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Highs and Lows of Bond Lengths: Is There Any Limit?
Álvaro Lobato,Miguel A. Salvadó,J. Manuel Recio,Mercedes Taravillo,Valentín G. Baonza,Valentín G. Baonza +5 more
TL;DR: In this article, two distinct points on the potential energy curve (PEC) of a pairwise interaction, the zero energy crossing point and the point where the stretching force constant vanishes, are defined and correlated with topological descriptors of electron-density-based scalar fields.
Journal ArticleDOI
Probing Halogen Bonds by Scalar Couplings.
TL;DR: In this article, the authors demonstrate that scalar coupling constants (J) are modulated by halogen bonding and that the binding-induced magnitude change of one-bond couplings correlates to the interaction strength.
Journal ArticleDOI
Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms
TL;DR: In this article, the effect of complexation with Lewis acids on the tautomeric equilibrium of a derivative of pyridoxal has been explored using density functional theory.
Journal ArticleDOI
Magnesium Bonds: From Divalent Mg Centres to Trigonal and Tetrahedral Coordination
Journal ArticleDOI
Theoretical Insights into Halogenated Uranium Cyanide/Isocyanide Compounds.
TL;DR: Two kinds of halogenated uranium cyanide/isocyanide compounds, XUCN and XUNC, formed by the insertion of uranium atom into X-C(N) bonds of XCN were investigated by DFT and ab initio methods and it is revealed that the isocyanides exhibits better donation performance than the cyanide.
References
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Journal ArticleDOI
General atomic and molecular electronic structure system
Michael W. Schmidt,Kim K. Baldridge,Jerry A. Boatz,Steven T. Elbert,Mark S. Gordon,Jan H. Jensen,Shiro Koseki,Nikita Matsunaga,Kiet A. Nguyen,Shujun Su,Theresa L. Windus,Michel Dupuis,John A. Montgomery +12 more
TL;DR: A description of the ab initio quantum chemistry package GAMESS, which can be treated with wave functions ranging from the simplest closed‐shell case up to a general MCSCF case, permitting calculations at the necessary level of sophistication.
Journal ArticleDOI
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
Journal ArticleDOI
Note on an Approximation Treatment for Many-Electron Systems
Chr. Møller,Milton S. Plesset +1 more
TL;DR: In this article, a perturbation theory for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation was developed, and it was shown by this development that the first order correction for the energy and the charge density of the system is zero.
Book
Atoms in molecules : a quantum theory
TL;DR: In this article, the quantum atom and the topology of the charge desnity of a quantum atom are discussed, as well as the mechanics of an atom in a molecule.
Journal ArticleDOI
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
TL;DR: In this paper, a modified basis set of supplementary diffuse s and p functions, multiple polarization functions (double and triple sets of d functions), and higher angular momentum polarization functions were defined for use with the 6.31G and 6.311G basis sets.