Comparison of density functional and Hartree-Fock average local ionization energies on molecular surfaces

Politzer, Peter; Abu-Awwad, Fakher; Murray, Jane S.

doi:10.1002/(sici)1097-461x(1998)69:4<607::aid-qua18>3.0.co;2-w

Cited by 157 publications

(85 citation statements)

References 30 publications

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“…34 However, many studies have reported their similarity with the HF orbitals, 35,36 and KS orbital energies can additionally be used to approximate the IP. 37,38 Although the previous study 37 reports a strong correlation (R 2 ≈ 0.99) between HF and DFT methods for E HOMO values for 11 substituted benzenes, an extensive comparative study of E HOMO values for a large number of aromatic compounds with diverse substituents (N = 112 in the present study) has not been performed yet. To our knowledge, moreover, the comparison between the HF and DFT methods has not been yet investigated for olefins and amines for which the E NBO is to be correlated with the corresponding k O 3 values.…”

Section: ■ Introductionmentioning

confidence: 85%

Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals

Lee

Zimmermann-Steffens

Arey

et al. 2015

Environ. Sci. Technol.

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Second-order rate constants (kO3) for the reaction of ozone with micropollutants are essential parameters for the assessment of micropollutant elimination efficiency during ozonation in water and wastewater treatment. Prediction models for kO3 were developed for aromatic compounds, olefins, and amines by quantum chemical molecular orbital calculations employing ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods. The kO3 values for aromatic compounds correlated well with the energy of a delocalized molecular orbital first appearing on an aromatic ring (i.e., the highest occupied molecular orbital (HOMO) or HOMO-n (n ≥ 0) when the HOMO is not located on the aromatic ring); the number of compounds tested (N) was 112, and the correlation coefficient (R(2)) values were 0.82-1.00. The kO3 values for olefins and amines correlated well with the energy of a localized molecular orbital (i.e., the natural bond orbital (NBO)) energy of the carbon-carbon π bond of olefins (N = 45, R(2) values of 0.82-0.85) and the NBO energy of the nitrogen lone-pair electrons of amines (N = 59, R(2) values of 0.81-0.83), respectively. Considering the performance of the kO3 prediction model and the computational costs, the HF/6-31G method is recommended for all aromatic groups and olefins investigated herein, whereas the HF/MIDI!, HF/6-31G*, or HF/6-311++G** methods are recommended for amines. Based on their mean absolute errors, the above models could predict kO3 within a factor of 4, on average, relative to the experimentally determined values. Overall, good correlations were also observed (R(2) values of 0.77-0.96) between kO3 predictions by quantum molecular orbital descriptors in this study and by the Hammett (σ) and Taft (σ*) constants from previously developed quantitative structure-activity relationship (QSAR) models. Hence, the quantum molecular orbital descriptors are an alternative to σ and σ*-values in QSAR applications and can also be utilized to estimate unknown σ or σ*-values.  .

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Section: ■ Introductionmentioning

confidence: 85%

Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals

Lee

Zimmermann-Steffens

Arey

et al. 2015

Environ. Sci. Technol.

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“…18 Politzer et al showed that the experimental IPs for 9 monosubstituted benzene derivatives linearly correlate with both the HF HOMO energies and the DFT HOMO energies. 19 In addition, by comparing the KS orbital energies ( i KS ) with the HF orbital energies ( i HF ), Stowasser and Hoffman found a linear relationship for | i KSi HF | vs i HF . 20 To improve the agreement of the HOMO energy with the first IP, new functionals and approximations for the KS potential have been tested which account for the effects of selfinteraction, [21][22][23] which is ignored in all of the commonly used functionals.…”

Section: Introductionmentioning

confidence: 99%

Ionization Potential, Electron Affinity, Electronegativity, Hardness, and Electron Excitation Energy: Molecular Properties from Density Functional Theory Orbital Energies

2003

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Representative atomic and molecular systems, including various inorganic and organic molecules with covalent and ionic bonds, have been studied by using density functional theory. The calculations were done with the commonly used exchange-correlation functional B3LYP followed by a comprehensive analysis of the calculated highest-occupied and lowest-unoccupied Kohn-Sham orbital (HOMO and LUMO) energies. The basis set dependence of the DFT results shows that the economical 6-31+G* basis set is generally sufficient for calculating the HOMO and LUMO energies (if the calculated LUMO energies are negative) for use in correlating with molecular properties. The directly calculated ionization potential (IP), electron affinity (EA), electronegativity ( ), hardness (η), and first electron excitation energy (τ) are all in good agreement with the available experimental data. A generally applicable linear correlation relationship exists between the calculated HOMO energies and the experimental/calculated IPs. We have also found satisfactory linear correlation relationships between the calculated LUMO energies and experimental/calculated EAs (for the bound anionic states), between the calculated average HOMO/LUMO energies and values, between the calculated HOMO-LUMO energy gaps and η values, and between the calculated HOMO-LUMO energy gaps and experimental/ calculated first excitation energies. By using these linear correlation relationships, the calculated HOMO and LUMO energies can be employed to semiquantitatively estimate ionization potential, electron affinity, electronegativity, hardness, and first excitation energy.

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“…Politzer and co-workers [1][2][3][4][5] were the first to recognize the significance of this quantity and studied it extensively in the framework of approximate Hartree-Fock (HF) and Kohn-Sham (KS) methods (see Refs. 6-8 for reviews).…”

Section: Introductionmentioning

confidence: 99%

“…The negative of the generalized ALEE, I (r) = −¯ (r), may be thought of as a particular generalization of the average local ionization energy of Politzer and co-workers. [1][2][3][4][5][6][7][8] …”

Section: Introductionmentioning

confidence: 99%

Average local ionization energy generalized to correlated wavefunctions

Ryabinkin

Staroverov

2014

The Journal of Chemical Physics

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The average local ionization energy function introduced by Politzer and co-workers [Can. J. Chem. 68, 1440 (1990)] as a descriptor of chemical reactivity has a limited utility because it is defined only for one-determinantal self-consistent-field methods such as the Hartree-Fock theory and the Kohn-Sham density-functional scheme. We reinterpret the negative of the average local ionization energy as the average total energy of an electron at a given point and, by rewriting this quantity in terms of reduced density matrices, arrive at its natural generalization to correlated wavefunctions. The generalized average local electron energy turns out to be the diagonal part of the coordinate representation of the generalized Fock operator divided by the electron density; it reduces to the original definition in terms of canonical orbitals and their eigenvalues for one-determinantal wavefunctions. The discussion is illustrated with calculations on selected atoms and molecules at various levels of theory.

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Comparison of density functional and Hartree-Fock average local ionization energies on molecular surfaces

Cited by 157 publications

References 30 publications

Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals

Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals

Ionization Potential, Electron Affinity, Electronegativity, Hardness, and Electron Excitation Energy: Molecular Properties from Density Functional Theory Orbital Energies

Average local ionization energy generalized to correlated wavefunctions

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