The use of the electronegativity equalization principle to study charge distributions in enzymes: application to dipeptides

Baeten, A.; Geerlings, Pau̧l

doi:10.1016/s0166-1280(98)00334-0

Cited by 9 publications

(18 citation statements)

References 21 publications

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“…This work is part of our ongoing interest in the development/use of DFT-based reactivity descriptors (conceptual DFT) [63][64][65][66] and their application to systems of biological interest. [67][68][69][70][71][72][73][74] Theory and Computational Details Geometry Optimization and Level of Calculation. Post Hartree-Fock methods as Møller-Plesset perturbation theory (MP) 75 and coupled cluster theory 76,77 have been tested in the past for their ability to describe the interaction energy between two benzene rings, RNA/DNA base pairs, and aromatic amino acids.…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, the MEP has been known for a long time to be a reliable descriptor of the hydrogen bond strength: the deeper the electrostatic potential, the stronger the electrostatic interaction with water molecules and with hydrogen bond donors in general. − The polarizability, related to the London dispersion energy, and density functional theory (DFT) based reactivity descriptors such as the global and local hardnesses of the isolated substituted benzenes were used in order to assess the amplitude of the stacking interaction. This work is part of our ongoing interest in the development/use of DFT-based reactivity descriptors (conceptual DFT) − and their application to systems of biological interest. − …”

Section: Introductionmentioning

confidence: 99%

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Influence of Stacking on Hydrogen Bonding: Quantum Chemical Study on Pyridine−Benzene Model Complexes

et al. 2004

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The present work focuses on the influence of aromatic stacking on the ability of an aromatic nitrogen base to accept a hydrogen bond. Substituent effects were studied at the MP2 level for 10 complexes of a substituted benzene stacked with pyridine in a parallel offset conformation. The interaction energies between each substituted benzene and pyridine were analyzed in terms of Hartree-Fock, correlation, and electrostatic contributions. It appears that the basicity of pyridine is directly related to the electrostatic interaction between the cycles. It increases with increasing electron donating character of the benzene substituents. Also, density functional theory based descriptors such as global and local hardnesses and the benzene ring polarizability are found to adequately predict the interaction energy. These findings may be important in the study of DNA/ RNA chains.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Stacking on Hydrogen Bonding: Quantum Chemical Study on Pyridine−Benzene Model Complexes

et al. 2004

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“…Constructing an electronegativity equalization scheme (EES), which demands an a priori knowledge of the charge distribution in the entire molecule would be pointless and unfeasible when the procedure is used for evaluating properties of large series of large molecules as typical EES strategies aim at. 45 The goal of the present paper is to show that by starting from the correct definition of the chemical potential and by using a similar type of modeled environment, one can estimate the charge transfer between two functional groups A and B forming the AB molecule by implicitly including the major part of the external potential effect. This no longer requires an a priori knowledge of the charge distribution in the entire molecule, nor calibration of multiple parameters.…”

Section: Introductionmentioning

confidence: 99%

A Group Electronegativity Equalization Scheme Including External Potential Effects

2006

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By calculating the electron affinity and ionization energy of different functional groups, CCSD electronegativity values are obtained, which implicitly account for the effect of the molecular environment. This latter is approximated using a chemically justified point charge model. On the basis of Sanderson's electronegativity equalization principle, this approach is shown to lead to reliable "group in molecule" electronegativities. Using a slight adjustment of the modeled environment and first-order principles, an electronegativity equalization scheme is obtained, which implicitly accounts for the major part of the external potential effect. This scheme can be applied in a predictive manner to estimate the charge transfer between two functional groups, without having to rely on cumbersome calibrations. A very satisfactory correlation is obtained between these charge transfers and those obtained from an ab initio calculation of the entire molecule.

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“…[41,42] There are several rules or methods to establish this principle which lead to the computation of molecular electronegativity. [43][44][45][46] One of them is based on the geometric mean rule according to which the absolute molecular electronegativity (χ GM ) is obtained as a geometric mean of each atom's electronegativity in a molecule. [46][47][48]…”

Section: Validation Of Electronegativity Equalization Principlementioning

confidence: 99%

A Scale of Atomic Electronegativity Based on Floating Spherical Gaussian Orbital Approach

2021

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Electronegativity (χ) is an old yet valuable concept having multidisciplinary applications. To advance the understanding of this concept, an electronegativity model has been proposed based on polarizability within the context of Floating Spherical Gaussian Orbital (FSGO) approach. The model provides atomic electronegativity scale for 120 elements. The calculated electronegativity presents marked periodicity and relates well with other electronegativity scales. Further, Electronegativity Equalization Principle is validated by the computed electronegativity data. The proposed scale has also been successfully applied to compute Fermi energy for some metal oxides. In accordance with the literature, this is the first FSGO-polarizability based model of electronegativity.

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The use of the electronegativity equalization principle to study charge distributions in enzymes: application to dipeptides

Cited by 9 publications

References 21 publications

Influence of Stacking on Hydrogen Bonding: Quantum Chemical Study on Pyridine−Benzene Model Complexes

Influence of Stacking on Hydrogen Bonding: Quantum Chemical Study on Pyridine−Benzene Model Complexes

A Group Electronegativity Equalization Scheme Including External Potential Effects

A Scale of Atomic Electronegativity Based on Floating Spherical Gaussian Orbital Approach

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