Correlations between molecular electrostatic potentials and some experimentally-based indices of reactivity

Murray, Jane S.; Brinck, Tore; Grice, M. Edward; Politzer, Peter

doi:10.1016/0166-1280(92)87156-t

Cited by 118 publications

(70 citation statements)

References 35 publications

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“…Here, we find that the locations of these minima do not change significantly from compound to compound and that the main differences are in the absolute values and are mainly between compound 2 and all the others. In other words, there is no correlation between the activity and the extreme values and the locations of the MEP minima, although other workers ( [28]; see, also, e.g., [22,29]) have found such correlations for other drugs. Another feature is that the MEP minimum near 0 1 has a quite negative value (--0.050 au).…”

Section: Resultsmentioning

confidence: 96%

Hydrogen‐bonding effects, electrostatic potential, and the antitumor activity of flavone acetic acid and related compounds. I. Ab initio studies on the first stable conformations

Fang

Thomson

1995

Int J of Quantum Chemistry

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=Ab initio investigations have been carried out to account for the antitumor activity of flavone acetic acid (FAA) and related compounds. The hydrogen-bonding conformation was chosen for all the compounds and obtained through a restricted geometry optimization with the 3 -2 1~ basis set. Three key regions in the molecular electrostatic potential isosurfaces [V(r) --0.015 au] are found to be involved in the activity.

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Section: Resultsmentioning

confidence: 96%

Hydrogen‐bonding effects, electrostatic potential, and the antitumor activity of flavone acetic acid and related compounds. I. Ab initio studies on the first stable conformations

Fang

Thomson

1995

Int J of Quantum Chemistry

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“…More recently, we have focused upon the electrostatic potential V S (r) computed upon the molecular surface. Instead of defining this by means of a set of intersecting spheres, however, we follow Bader et al [28] in taking it to be the 0.001 au contour of the electronic density ρ(r) [29,30]. This has the advantage that the surface can reflect features specific to the particular molecule, e.g., lone pairs, strained bonds, etc.…”

Section: Methodology Electrostatic Potentialmentioning

confidence: 98%

Computational characterization of nucleotide bases: Molecular surface electrostatic potentials and local ionization energies, and local polarization energies

Murray

Peralta-Inga

Politzer

et al. 2001

Int J of Quantum Chemistry

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Electrostatic potentials and local ionization energies have been computedat the HF/6-31G * level on the molecular surfaces of the five nucleotide bases. The potentials are analyzed in terms of their most positive and negative values as well as several statistically defined quantities that reflect their patterns over the entire surface. Considerable charge separation and variability are found for all five molecules. The results are consistent with the base pairing that is known to occur. The observed reactive behavior toward electrophiles can be interpreted in terms of the complementary roles of the surface potential and the local electron lability. Local polarization energies, corresponding to a test charge being placed at specific points above the molecules, are also calculated (HF/6-31+G * ), and their relationship to the local ionization energies is examined.

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“…Electrostatic potentials: Since the original work of Murray and Politzer, [13,15,35,36] it has been consistently shown that FD relationships exist between the hydrogen-bond basicity and the minimum electrostatic potential in the vicinity of the nitrogen atom of N-heterocycles, [14,23] nitriles [37] and amines. [16,38] The so-called V s,min values are calculated at the molecular surface, as defined by the 0.001 e Bohr À3 contour of the electronic density, [39] with the Spartan program.…”

Section: Methodsmentioning

confidence: 99%

A Theoretical Evaluation of the pK_HBand Δ$H{{{\,\ominus}\hfill \atop {\rm HB}\hfill}}}$ Hydrogen‐Bond Scales of Nitrogen Bases

Besseau

Graton

Berthelot

2008

Chemistry A European J

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The experimental pKHB hydrogen-bond (HB) basicity scale and the corresponding DeltaH[symbol: see text]HB enthalpic scale of nitrogen compounds are extended and analysed in light of simple theoretical descriptors using the B3LYP density functional method and a medium-size basis set (6-31+G(d,p)).The selected training set includes 59 monofunctional unhindered nitrogen bases for which homogeneous and accurate experimental pKHB and DeltaH[symbol: see text]HB data have been determined by means of the association equilibrium of the bases with a reference hydrogen-bond acid, 4-fluorophenol, in CCl4. The three hybridisation states encountered in the nitrogen atom, sp, sp2 and sp3, are equally represented in this data set. A proper estimation of their experimental enthalpy (DeltaH[symbol: see text]HB) is directly attainable from the theoretical enthalpy of the complexation reaction with hydrogen fluoride (DeltaH[symbol: see text](HF)). However, a second parameter is required to calculate with good accuracy the experimental free energy of association represented by pKHB. About 99% of the variance of the pKHB scale is described by a bilinear equation using the minimum electrostatic potential (Vs,min) of the monomer in addition to the interaction energy (D0(HF). The equations are tested for an external set of 99 additional compounds including very different nitrogen bases such as ortho-substituted pyridines, polyazines and azoles.Theoretical calculations give a reliable estimation of hydrogen-bond basicity provided that the populations of the different isomers of the bases are taken into account by using the Boltzmann law, and that a specific halogen-bond interaction with the solvent CCl4 is considered for polybasic molecules.The pKHB scale can thus be extended to important classes of species experimentally inaccessible in CCl4, to polynitrogen compounds and to molecules of biological significance.

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Correlations between molecular electrostatic potentials and some experimentally-based indices of reactivity

Cited by 118 publications

References 35 publications

Hydrogen‐bonding effects, electrostatic potential, and the antitumor activity of flavone acetic acid and related compounds. I. Ab initio studies on the first stable conformations

Hydrogen‐bonding effects, electrostatic potential, and the antitumor activity of flavone acetic acid and related compounds. I. Ab initio studies on the first stable conformations

Computational characterization of nucleotide bases: Molecular surface electrostatic potentials and local ionization energies, and local polarization energies

A Theoretical Evaluation of the pK_HBand Δ$H{{{\,\ominus}\hfill \atop {\rm HB}\hfill}}}$ Hydrogen‐Bond Scales of Nitrogen Bases

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Correlations between molecular electrostatic potentials and some experimentally-based indices of reactivity

Cited by 118 publications

References 35 publications

Hydrogen‐bonding effects, electrostatic potential, and the antitumor activity of flavone acetic acid and related compounds. I. Ab initio studies on the first stable conformations

Hydrogen‐bonding effects, electrostatic potential, and the antitumor activity of flavone acetic acid and related compounds. I. Ab initio studies on the first stable conformations

Computational characterization of nucleotide bases: Molecular surface electrostatic potentials and local ionization energies, and local polarization energies

A Theoretical Evaluation of the pKHBand Δ$H{{{\,\ominus}\hfill \atop {\rm HB}\hfill}}}$ Hydrogen‐Bond Scales of Nitrogen Bases

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A Theoretical Evaluation of the pK_HBand Δ$H{{{\,\ominus}\hfill \atop {\rm HB}\hfill}}}$ Hydrogen‐Bond Scales of Nitrogen Bases