Correlations between Fukui Indices and Reactivity Descriptors Based on Sanderson’s Principle

Sánchez‐Márquez, Jesús

doi:10.1021/acs.jpca.9b05571

Cited by 18 publications

(14 citation statements)

References 65 publications

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“…In a previous paper, we studied some possibilities for deriving a local electrophilicity and concluded that eq seems to be not only very simple, but at the same time a very reliable approach to this important property: where the term f k α (α = + , – or 0) corresponds to local Fukui functions, which are normally defined as: and (for neutral or radical attacks), where q k ( N 0 – 1), q k ( N 0 ), and q k ( N 0 + 1) are the electron populations associated with the k th atom (in the cation, neutral molecule, and anion, respectively). The electron populations should be calculated by using a particular population analysis (Hirshfeld’s analysis − as an example).…”

Section: Methodsmentioning

confidence: 99%

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On Electronegativity, Hardness, and Reactivity Descriptors: A New Property-Oriented Basis Set

et al. 2020

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In this study, various ways of calculating electronegativity are analyzed after a brief summary of the evolution of this concept. We point out that some commonly used basis sets to calculate this parameter, such as 6-311G(d), provide results with an extraordinarily high margin of error. Therefore, a correction to the 6-311G(d) basis set is proposed that leads to calculations of electronegativity and hardness with a quality similar to those obtained with much broader basis sets, such as Aug-cc-pVQZ and Aug-cc-pV5Z. Since the calculation effort of the proposed basis is small, it can be applied to the accurate calculation of electronegativity and hardness in relatively large systems. It has also been tested in the calculation of reactivity indices and we have obtained results similar to those of the Aug-cc-pV5Z basis set. Finally, we have studied the densities corresponding to the frontier molecular orbitals in a representative sample set of molecules, using both the improved and other standard basis sets, and we have verified that the quality level of the proposed basis set is clearly better than that of standard basis sets with a similar calculation effort.

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Section: Methodsmentioning

confidence: 99%

“…In a previous paper, 24 we studied some possibilities for deriving a local electrophilicity 25 and concluded that eq 20 seems to be not only very simple, but at the same time a very reliable approach to this important property:…”

Section: Introductionmentioning

confidence: 99%

On Electronegativity, Hardness, and Reactivity Descriptors: A New Property-Oriented Basis Set

et al. 2020

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“…In Reference [32], a methodology was defined to obtain bond reactivity indices for the NBOs (

f_{i}^{- (NBO)}

and

f_{i}^{+ (NBO)}

indices in Equations () and ()) that is based on the regression that can be seen in Equations () and (), which provide reactivity indices for bond orbitals instead of the atoms in the molecule. Bond index is not a new concept as it was previously proposed by Bultinck et al [33].…”

Section: Description and Fundamentals Of The New Model Why Choose Nat...mentioning

confidence: 99%

“…The parabolic approximation [11] is usually expressed as:

Δ E \approx μ Δ N + \frac{1}{2} η Δ N^{2} .

But, in Reference [29], the author justifies the use of a cubic expansion of the shape:

Δ E_{A} \approx μ \cdot Δ N_{A} + \frac{1}{2} η_{A} Δ N_{A}^{2} + \frac{1}{6} \cdot {normalΩ}_{A} \cdot Δ N_{A}^{3},

in the local case (atoms in the molecule), where

{normalΩ}_{A} = {((), \frac{\partial^{3} Δ E_{A}}{\partial N_{A}^{3}})}_{Δ N = 0}

. Moreover, the local chemical potentials of the atoms in equilibrium (and the corresponding ions) should satisfy (principle of electronegativity equalization):

μ_{A}^{0} = μ_{B}^{0} = \dots = μ_{k}^{0} = μ,

μ_{A}^{+} = μ_{B}^{+} = \dots = μ_{k}^{+} = μ^{+},

μ_{A}^{-} = μ_{B}^{-} = \dots = μ_{k}^{-} = μ^{-},

where A , B ,… k refer to the atoms of the molecule, and μ , μ + , and μ − to the global electronic chemical potentials of the neutral molecule, cation and anion, respectively.…”

Section: Introductionmentioning

confidence: 99%

Introducing a new model based on electronegativity equalization principle for the analysis of the natural bond orbital reactivity in the c‐DFT background

Sánchez‐Márquez

Cuenca

Núñez

et al. 2022

Int J of Quantum Chemistry

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Previous studies presented two independent models based on the equalization of electronegativity and on an alternative operative formula for the Fukui function. The current paper presents modifications to these models to obtain a new model for calculating the local energy derivatives (electronic chemical potential, local electronic hardness and local hypersoftness) and density (Fukui and dual descriptor indices) in natural bond orbitals for the study of chemical reactivity from the perspective of these orbitals (local electrophilicity and local maximum charge variation have also been deduced). We have radically changed the way of partitioning the electron density because the atomic model cannot distinguish between bonding and non‐bonding electron pairs, or between electrons with different types of bonds, however, this is possible with the model based on bond orbitals. In this respect, this model is ideal for organic reactions because of their correspondence with Lewis structures, which are simple but very useful for representing reaction mechanisms.

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“…Nucleophilic attack, f + (r) = q r (N+1)-q r (N) Electrophilic attack, f -(r) = q r (N) -q r (N-1) Radial attack, f o (r) = [q r (N+1)-q r (N-1)]/2 Dual descriptor, ∆f(r)= f + (r)-f -(r) where q r corresponds to atomic charge evaluated from mulliken charge, N corresponds to atomic charge, (N+1) corresponds to cationic state and (N-1) corresponds to anionic state [48][49][50]. Regions in chemical species with the highest values of the Fukui function (fj) demonstrate significant reactivity for comparable attacks, according to Parr and Yang et al [50].…”

Section: Fukui Functionmentioning

confidence: 99%

Structure Activity Relationship, Topological Analysis and Molecular Docking Analysis of Pharmaceutical Molecule 2356 -Tetrafluoro-4-Pyridine Carbonitrile

Mary

Ramkumar

Benisha

2021

JPRI

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The theoretical vibrational spectral features of 2,3,5,6 Tetrafluoro-4-pyridinecarbonitrile were explored and compared with experimental results. The geometrical parameters, vibrational wavenumbers, bonding features and Energies were calculated at the B3LYP level with the basis set 6-311++G(d,p) levels. The calculated wavenumbers, vibrational energy distribution Analysis (VEDA), potential energy distributions (PEDs), and vibrational spectra were used to suggest reliable vibrational assignments. Molecular Electrostatic Potential investigations revealed the reactive zones around the molecule. The computed HOMO-LUMO energies were -8.369 and -3.380 eV, respectively, indicating charge transfer inside the molecule. The charge transfer of charge due to intra molecule interactions has been explained using naturalbond orbital analysis. The ELF and LOL calculations were provide a visual aid for interpreting the results of electronic structure. The molecular docking approach was used to find the optimal ligand–protein orientation using the ligand 2,3,5,6 Tetrafluoro-4 pyridinecarbonitrile, which was docked with five distinct proteins. The main aim of the present study is to evaluate the biological activity of the selected compound using theoretical calculations.

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Correlations between Fukui Indices and Reactivity Descriptors Based on Sanderson’s Principle

Cited by 18 publications

References 65 publications

On Electronegativity, Hardness, and Reactivity Descriptors: A New Property-Oriented Basis Set

On Electronegativity, Hardness, and Reactivity Descriptors: A New Property-Oriented Basis Set

Introducing a new model based on electronegativity equalization principle for the analysis of the natural bond orbital reactivity in the c‐DFT background

Structure Activity Relationship, Topological Analysis and Molecular Docking Analysis of Pharmaceutical Molecule 2356 -Tetrafluoro-4-Pyridine Carbonitrile

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