The electrostatic potential: an overview

Murray, Jane S.; Politzer, Peter

doi:10.1002/wcms.19

Cited by 1,093 publications

(668 citation statements)

References 67 publications

(104 reference statements)

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“…H 2 O adsorbs O-down to the V S,max (and E S,min ) sites with the optimized position of the interacting H 2 O deviating little from the V S,max (and E S,min ) positions (see also Section 4.3). H-down adsorption (∆E int = −0.27 eV) takes place at the V S,min sites, where the most prominent V S,min corresponds to the three-fold hollow h 5-10-12 site-this adsorption mode is in line with previous reports of H 2 O interactions with Cu nanoclusters [5,58].…”

Section: Cu 13 and Pt 7 Cusupporting

confidence: 90%

“…Correspondingly, minima in V S (r), i.e., V S,min , indicate sites prone to interaction with electrophiles (Lewis acids). V S (r) has been employed extensively in the study of molecular interactions including hydrogen and halogen bonding, biomolecular recognition interaction, estimations of pK A and molecular reactivity [2].…”

Section: Theorymentioning

confidence: 99%

“…These have been widely used to rationalize molecular interaction behavior and reactivity [2]. In the present contribution we introduce new categories of σ-holes based on the electronic origin of the V S,max ; if the V S,max arises primarily as a consequence of electron deficiencies in the valence s-orbitals of the compound, we shall denote it an σ s -hole.…”

Section: Introductionmentioning

confidence: 99%

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σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity

2017

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Understanding the molecular interaction behavior of transition metal nanoclusters lies at the heart of their efficient use in, e.g., heterogeneous catalysis, medical therapy and solar energy harvesting. For this purpose, we have evaluated the applicability of the surface electrostatic potential [V S (r)] and the local surface electron attachment energy [E S (r)] properties for characterizing the local Lewis acidity of a series of low-energy TM 13 transition metal nanoclusters (TM = Au, Cu, Ru, Rh, Pd, Ir, Pt, Co), including also Pt 7 Cu 6 . The clusters have been studied using hybrid Kohn-Sham density functional theory (DFT) calculations. The V S (r) and E S (r), evaluated at 0.001 a.u. isodensity contours, are used to analyze the interactions with H 2 O. We find that the maxima of V S (r), σ-holes, are either localized or diffuse. This is rationalized in terms of the nanocluster geometry and occupation of the clusters's, p and d valence orbitals. Our findings motivate a new scheme for characterizing σ-holes as σ s (diffuse), σ p (localized) or σ d (localized) depending on their electronic origin. The positions of the maxima in V S (r) (and minima in E S (r)) are found to coincide with O-down adsorption sites of H 2 O, whereas minima in V S (r) leads to H-down adsorption. Linear relationships between V S,max (and E S,min ) and H 2 O interaction energies are further discussed.

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Section: Cu 13 and Pt 7 Cusupporting

confidence: 90%

Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity

2017

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“…All carbon atoms have negative charges except for the cases of C17 and C11, which would be responsible for nucleophilic attack sites. Electrostatic potential (ESP) on molecular van der Waals (vdW) surface is important to study and predict the intermolecular interactions [28][29][30]. It is well known that intermolecular recognition and electrostatic dominated noncovalent interactions tend to occur in terms of electrostatically complementary manner.…”

Section: Mulliken Atomic Charges and Molecular Electrostaticmentioning

confidence: 99%

Synthesis, Crystal Structure, and DFT Study of Ethyl 1-(2-(Hydroxyimino)-2-phenylethyl)-3-phenyl-1H-pyrazole-5-carboxylate

Zhou

Zheng²,

Yan

et al. 2017

Journal of Chemistry

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The crystal structure of ethyl 1-(2-(hydroxyimino)-2-phenylethyl)-3-phenyl-1H-pyrazole-5-carboxylate has been determined by Xray single crystal diffraction. The crystal of the title compound is the monoclinic space group P2/c with unit cell parameters of = 8.634(2)Å, = 9.616(2)Å, = 22.190(3)Å, = 99.265(2) ∘ , = 1818.3(4)Å 3 , and = 4. The dihedral angles formed by the planes of the central pyrazole ring and the adjacent benzene rings are 73.60(7) ∘ and 3.55(7) ∘ , respectively. The combination of the weak intermolecular C-H⋅ ⋅ ⋅ O and N-H⋅ ⋅ ⋅ O hydrogen-bonding interactions stabilizes the crystal packing. The geometries of its Z and E isomers and the corresponding transition state (TS), as well as the dimer of its Z isomer, are optimized using the B3LYP hybrid functional coupled with def-TZVP triple-zeta polarized basis set. The bond angles and bond lengths of the optimized structure of Z dimer are very consistent with those of its single crystal parameters. Double-hybrid functional PWPB95-D3 in combination with very highly accurate basis set def2-QZVP is employed to evaluate accurate energy of each isomer and TS. The calculated equilibrium constant between Z and E isomers corresponds to the [Z]/[E] ratio of 4.29. Mulliken atomic charges and electrostatic potential (ESP) on molecular van der Waals (vdW) surface are calculated in order to study and predict the intermolecular interactions. The molecular total energies and frontier orbital analysis are also discussed.

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“…In particular electrostatic interactions have been successfully explained by the use of the molecular electrostatic potential [6,7].…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study of the Chemical Reactivity of Neohesperidin Dihydrochalcone Through Conceptual DFT Descriptors

Glossman‐Mitnik¹,

Fraua²,

Muñoz³

et al. 2017

SDRP-JCCMM

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ABSTRACT:The Minnesota family of density functionals has been assessed for the calcula-tion of the molecular structure and properties of Neohesperidin Dihydrochalcone (NHDC) that can be an interesting sweetener with potential to act as inhibitors of the nonenzimatic glycation of amino acids and proteins, both acting as antioxidant and perhaps as chelating agents for metallic ions, like Cu, Al and Fe. The chemical reactivity descriptors have been calculated through Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices and the dual descriptor f(2)(r). A comparison between the descriptors calculated through vertical energy values and those arising from the "Koopmans' theorem in DFT" approximation have been performed in order to check for the validity of the last procedure and the accuracy of the studied density functionals.

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The electrostatic potential: an overview

Cited by 1,093 publications

References 67 publications

σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity

σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity

Synthesis, Crystal Structure, and DFT Study of Ethyl 1-(2-(Hydroxyimino)-2-phenylethyl)-3-phenyl-1H-pyrazole-5-carboxylate

A Theoretical Study of the Chemical Reactivity of Neohesperidin Dihydrochalcone Through Conceptual DFT Descriptors

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