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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Polar coordinate representation of Hb(rc) versus (h2/8m)nabla2rhob(rc) at BCP in AIM analysis: classification and evaluation of weak to strong interactions.
TL;DR: Polar coordinate (R, theta) representation is proposed for the plot of Hb(rc) versus (h2/8m)nabla2rhob(RC) in AIM analysis to classify, evaluate, and understand weak to strong interactions in a unified way and in more detail.
Journal ArticleDOI
How Reliable Are Intermolecular Interaction Energies Estimated from Topological Analysis of Experimental Electron Densities
TL;DR: In this article, the reliability of intermolecular interaction energies estimated from critical point properties of experimental electron densities was examined and it was shown that they are inherently unreliable, typically underestimating but sometimes overestimating more reliable values.
Journal ArticleDOI
Interplay of F-H···F hydrogen bonds and P···N pnicogen bonds.
TL;DR: The NBO analysis indicates that the N(lp → P-Fσ* charge-transfer transition has a much greater stabilizing effect than the P(lp) → N-Fρσ* transition, which leads to shorter P···N distances, increased strength of P··N bonds, and synergistic energetic effects.
Journal ArticleDOI
Significance of hydrogen bonding and other noncovalent interactions in determining octahedral tilting in the CH 3 NH 3 PbI 3 hybrid organic-inorganic halide perovskite solar cell semiconductor
TL;DR: The prevailing view of hydrogen bonding in CH3NH3PbI3 is misleading as it does not alone determine the a−b+a− tilting pattern of the PbI64− octahedra, so these interactions should not be regarded as the sole determinants of octahedral tilting since lattice dynamics is known to play a critical role.
Journal ArticleDOI
Hydrogen bonds: relation between lengths and electron densities at bond critical points
TL;DR: In this paper, the electron densities for a number of molecules with either inter- or intra-molecular hydrogen bonds are analyzed using the theory of atoms in molecules using second order Moller Plesset and density functional methods.
References
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General atomic and molecular electronic structure system
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Note on an Approximation Treatment for Many-Electron Systems
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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.