Journal ArticleDOI
The electrostatic potential at atomic sites as a reactivity index in the hydrogen bond formation
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In this paper, the authors present results from computational studies by molecular orbital and density functional theories on several series of hydrogen-bonded complexes, which aim at quantifying the reactivity of molecules for the complexation process.Abstract:
The paper reviews results from computational studies by molecular orbital and density functional theories on several series of hydrogen bonded complexes. These studies aim at quantifying the reactivity of molecules for the complexation process. Excellent linear relationships are found between the electrostatic potential values at the sites of the electron donor and electron accepting atoms and the energy of hydrogen bond formation (ΔE). The series studied are: (a) complexes of R–CHO and R–CN molecules with hydrogen fluoride; (b) complexes of mono-substituted acetylene derivatives with ammonia; (c) (HCN)n hydrogen bonded cluster for n=2–7. All 22 studied complexes of carbonyl and nitrile compounds with hydrogen fluoride fall in the same dependence between the energy of hydrogen bond formation and the electrostatic potential at the atomic site of the carbonyl oxygen and nitrile nitrogen atoms, with linear regression correlation coefficient r=0.979. In the case of complexes of mono-substituted acetylene and diacetylene derivatives with NH3, the correlation coefficient for the dependence between the electrostatic potential at the acidic hydrogen atom and ΔE equals 0.996. For the series of hydrogen bonded (HCN)n clusters, the correlation coefficient for the relationship between the electrostatic potential at the end nitrogen atom and ΔE is r=0.9996. Similarly, the analogous relationship with the electrostatic potential at the end hydrogen atom has a regression coefficient equal to 0.9994. The dependencies found are theoretically substantiated by applying the Morokuma energy decomposition scheme. The results show that the molecular electrostatic potential at atomic sites can be successfully used to predict the ability of molecules to form hydrogen bonds.read more
Citations
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Journal ArticleDOI
Topological Descriptors of the Electron Density and the Electron Localization Function in Hydrogen Bond Dimers at Short Intermonomer Distances
TL;DR: In this article, the topology of the electron density ρ(r) and electron localization function η (r) gradient fields were obtained for short intermonomer distances.
Journal ArticleDOI
A Molecular Electrostatic Potential Analysis of Hydrogen, Halogen, and Dihydrogen Bonds
TL;DR: Hydrogen, halogen, and dihydrogen bonds in weak, medium and strong regimes have been investigated for several intermolecular donor-acceptor (D-A) complexes at ab initio MP4//MP2 method coupled with atoms-in-molecules and molecular electrostatic potential (MESP) approaches and MESP provides a clear evidence for hydrogen, hal gas bond formation.
Journal ArticleDOI
Definition of a nucleophilicity scale.
TL;DR: The results suggest that the Legon and Millen nucleophilicity scale and the electrostatic potential derived scales can describe in good approximation the reactivity order of the nucleophiles only when the interactions with a probe electrophile is of the hard-hard type.
Journal ArticleDOI
An efficient computational approach for the evaluation of substituent constants.
TL;DR: Theoretical computations to assess the influence of water solvent using the SCIPCM method showed that the solvent enhances the overall effect of polar substituents by about 30% and the relative values of the sigma(0) constants are predominantly determined by intramolecular influences.
Journal ArticleDOI
Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity
TL;DR: In this paper , a rigorous mapping of the molecular electrostatic potential (MESP) topology is achieved by computing both ∇V(r) data and the elements of the Hessian matrix at the critical points where ∆V( r) = 0, and the electron-rich regions such as lone pair and π-bonds show (3, +3) minimum (Vmin) CPs.
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Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis
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