On the condensed Fukui function

Fuentealba, Patricio; Pérez, Patricia; Contreras, Renato

doi:10.1063/1.1305879

Cited by 368 publications

(226 citation statements)

References 30 publications

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“…This basis set, featuring both polarized and diffuse orbitals, has been proved to be well suited for investigating systems with delocalized charges [18]. The most probable protonation sites of the molecules were determined through analysis of the electrophilic Fukui function [19]. The optimized structures were characterized by harmonic frequency analysis as local minima (all frequencies real).…”

Section: Methodsmentioning

confidence: 99%

“…In this context, local reactivity indices such as the atomic nucleophilic indices (f k -), also known as electrophilic Fukui functions, provide an interesting alternative way to identify the most probable sites of protonation [19]. Recently, this methodology has been employed to identify the protonation sites in a series of natural and synthetic compounds [6,29,30].…”

Section: Protonation Sitesmentioning

confidence: 99%

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Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Butler

Máñez

Cabrera

2011

J. Am. Soc. Mass Spectrom.

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Differentiation between two isomers of hydroxypyridine N-oxide according to the metal cation adducts generated by electrospray ionization (ESI) was investigated for different metal cations, namely Mg (II), Al (III), Ca (II), Sc (III), Fe (III), Co (II), Ni (II), Cu (II), Zn (II), Ga (III), besides the diatomic cation VO(IV). Protonated molecules of the isomeric hydroxypyridine N-oxides as well as the singly/doubly charged adducts formed from neutral or deprotonated ligands and a doubly/ triply charged cation were produced in the gas phase using ESI, recording mass spectra with different metal ions for each isomer. While complex formation was successful for 2-hydroxypyridine N-oxide with trivalent ions, in the case of 3-hydroxypyridine N-oxide, only peaks related to the protonated molecule were present. On the other hand, divalent cations formed specific species for each isomer, giving characteristic spectra in every case. Hence, differentiation was possible irrespective of the metal cation utilized. In addition, quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed in order to gain insight into the different complexation of calcium(II) with the isomers of hydroxypyridine N-oxide. The relative stability in the gas phase of the neutral complexes of calcium made up of two ligands, as well as the singly charged and doubly charged complexes, was investigated. The results of these calculations improved the understanding of the differences observed in the mass spectra obtained for each isomer.

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Section: Methodsmentioning

confidence: 99%

Section: Protonation Sitesmentioning

confidence: 99%

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Butler

Máñez

Cabrera

2011

J. Am. Soc. Mass Spectrom.

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“…25,26 On the other hand, there are numerical indications that the Hirshfeld charge scheme, 27 based on a stockholder idea, yields only positive Fukui functions. 4 -6,23,24,28 Negative values in other studies are then usually attributed to the characteristics of the population analysis partition scheme used.…”

Section: ͑2͒mentioning

confidence: 99%

“…[23][24][25][26] A negative Fukui function value means that when adding an electron to the molecule, in some spots the electron density is reduced, alternatively when removing an electron from the molecule, in some spots the electron density grows larger. This is counterintuitive.…”

Section: ͑2͒mentioning

confidence: 99%

Negative Fukui functions: New insights based on electronegativity equalization

Bultinck

Carbó‐Dorca

Langenaeker³

2003

The Journal of Chemical Physics

120

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Fukui functions have been calculated for large numbers of organic molecules, and were found to always be positive. Numeric and algebraic considerations allowed the identification of several boundary conditions for negative values for Fukui functions. Negative Fukui functions are found to be very unlikely, except when very short interatomic distances are present. Recent hypotheses concerning the occurrence of negative Fukui functions are strongly supported by the present approach.

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“…Assuming that the total energy E as a function of N and functional of v (r) is an exact differential, therefore, applying the Maxwell relations, equation 10 can be simplified to the following form [19],…”

Section: Quantum Chemical Studymentioning

confidence: 99%

Experimental and Quantum Chemical Studies on the Corrosion Inhibition Potential of Phthalic Acid for Mild Steel in 0.1 M H2SO4

PO¹

2015

Chem Sci J

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The corrosion inhibition potential of phthalic acid for mild steel in 0.1 M sulphuric acid was studied using experimental (weight loss, gasometric, FTIR and Scanning electron microscopy) and theoretical (semi empirical, Ab initio and DFT) approaches. Results obtained from weight loss measurements indicated that phthalic acid inhibited the corrosion of mild steel and recorded average and instantaneous maximum inhibition efficiencies of 55.48 and 87.34% at 303 K and at a concentration of 0.1 M respectively. Thermodynamic/adsorption considerations revealed that the adsorption of the inhibitor is exothermic, spontaneous and supported the mechanism of physical adsorption. The adsorption behaviour of the inhibitor was best described by the Langmuir adsorption model. FTIR spectra obtained from the corrosion product of mild steel in the absence and presence of the inhibitor revealed the existence of interaction between the inhibitor and the metal surface due to some shifts in the functional groups of the compound after adsorption. Scanning electron micrographs of the corroded metal (in the absence and presence of the inhibitor) revealed that phthalic acid prevented the corrosion of mild steel by forming protective coverage on the surface of the metal. Calculated quantum chemical parameters were found to be in good agreement with those reported for some good corrosion inhibitors. Although results obtained from Ab initio calculations for condensed Fukui functions were slightly at variance with those obtained from DFT calculations, considerations of Huckel charges on the atoms of the molecule, bond length, HOMO and LUMO molecular orbital plots clearly supported DFT results which indicated that the sites for nucleophilic and electrophilic attacks corresponded to atoms O(11) and C(4) respectively.

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On the condensed Fukui function

Cited by 368 publications

References 30 publications

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Negative Fukui functions: New insights based on electronegativity equalization

Experimental and Quantum Chemical Studies on the Corrosion Inhibition Potential of Phthalic Acid for Mild Steel in 0.1 M H2SO4

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