Average local ionization energy: A review

Politzer, Peter; Murray, Jane S.; Bulat, Felipe A.

doi:10.1007/s00894-010-0709-5

Cited by 400 publications

(231 citation statements)

References 128 publications

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“…Indeed, when the ΔE were expressed by double regression analysis as functions of the V S,min and the local ionization energies of the CN-Q carbons and the SiN-Q silicons, the relationship between predicted and computed ΔE had R 2 ¼ 0.99 [104]. (The local ionization energy was being used as a measure of polarizability [105].) The combination of a strong electric field produced by a large positive σ-hole V S,max plus a highly polarizable negative site (as indicated by a low local ionization energy) can result in polarization to an extent which might be described (in less physical and more ambiguous terms) as a significant degree of dative sharing of electrons, or coordinate covalence.…”

Section: "Anomalously" Strong Interactionsmentioning

confidence: 99%

σ-Hole Bonding: A Physical Interpretation

Politzer

Murray

Clark

2014

Topics in Current Chemistry

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117

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The anisotropic electronic densities of covalently-bonded Group IV-VII atoms frequently give rise to regions of positive electrostatic potential on the extensions of covalent bonds to these atoms. Through such positive "σ-holes," the atoms can interact attractively and highly directionally with negative sites such as the lone pairs of Lewis bases, anions, π electrons, etc. In the case of Group VII this is called "halogen bonding." Hydrogen bonding can be viewed as a less directional subset of σ-hole interactions. Since positive σ-holes often exist in conjunction with regions of negative potential, the atoms can also interact favorably with positive sites. In accordance with the Hellmann-Feynman theorem, all of these interactions are purely Coulombic in nature (which encompasses polarization and dispersion). The strength of σ-hole bonding increases with the magnitudes of the potentials of the positive σ-hole and the negative site; their polarizabilities must sometimes also be taken explicitly into account.

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Section: "Anomalously" Strong Interactionsmentioning

confidence: 99%

σ-Hole Bonding: A Physical Interpretation

Politzer

Murray

Clark

2014

Topics in Current Chemistry

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117

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“…The E(r) quantity can, in analogy to its nucleophilic counterpartĪ(r) (the average local ionization energy [40,41]), be decomposed into contributions from the electrostatic potential, the kinetic energy density t i (r) and the exchange-correlation potential [V XC (r)] by [33,42] …”

Section: Theorymentioning

confidence: 99%

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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“…The average local ionization energy can be used as a means of determining relative site reactivities [35]. The Ī(r) s with the lowest value and highest value are designated the Ī S,min and Ī S, max , respectively.…”

Section: Electrostatic Potentialmentioning

confidence: 99%

DFT, QTAIM, and NBO investigations of the ability of the Fe or Ni doped CNT to absorb and sense CO and NO

Zhang

Gong

2015

J Mol Model

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The structures and intramolecular interactions of complexes (FeCNT-CO, FeCNT-NO, NiCNT-CO, and NiCNT-NO) formed by the Fe or Ni doped single-wall carbon nanotube (FeCNT or NiCNT) and gas CO or NO were studied using density functional theory, quantum theory of atom in molecule (QTAIM), and natural bond orbital methods. The adsorption processes of CO and NO on surfaces of FeCNT and NiCNT are chemisorption, energetically favored, exothermic, and spontaneous. High temperature is not good for adsorption. Introducing NO more obviously elongates the distances between Fe/Ni and C atoms and decreases ∠CFe(Ni)C than adding CO. QTAIM analysis shows that the covalent bonding interactions of FeCNT-NO (NiCNT-NO) are stronger than that of FeCNT-CO (NiCNT-CO). NO plays a role of electron acceptor while CO is electron donator in complexes. Electrostatic interaction of FeCNT-NO (NiCNT-NO) is stronger than that of FeCNT-CO (NiCNT-CO). The stronger intramolecular interactions of FeCNT-NO and NiCNT-NO reveal that FeCNT and NiCNT are more effective to adsorb and sense NO than CO. CO and NO considerably change the electronic properties of FeCNT and NiCNT, which is useful for designing sensors for CO and NO.

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Average local ionization energy: A review

Cited by 400 publications

References 128 publications

σ-Hole Bonding: A Physical Interpretation

σ-Hole Bonding: A Physical Interpretation

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

DFT, QTAIM, and NBO investigations of the ability of the Fe or Ni doped CNT to absorb and sense CO and NO

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