Perspective on "Density functional approach to the frontier-electron theory of chemical reactivity"

Ayers, Paul W.; Levy, Mel

doi:10.1007/s002149900093

Cited by 422 publications

(81 citation statements)

References 36 publications

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“…Based on more intuitive considerations on the E = E(N) curve in the early days, its intrinsic value was stressed by the fundamental work by the famous Perdew, Parr, Levy, Balduz paper, 23,24 pointing out the continuous nature of the E = E(N) curve as a piecewise linear function in the canonical example. 25 Computational techniques yielding this property should, however, obey strict conditions and be of the many electron self-interaction free type 26 (for a recent in depth analysis see Refs. [27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Analytical evaluation of Fukui functions and real-space linear response function

Yang

Cohen

Proft

et al. 2012

The Journal of Chemical Physics

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Many useful concepts developed within density functional theory provide much insight for the understanding and prediction of chemical reactivity, one of the main aims in the field of conceptual density functional theory. While approximate evaluations of such concepts exist, the analytical and efficient evaluation is, however, challenging, because such concepts are usually expressed in terms of functional derivatives with respect to the electron density, or partial derivatives with respect to the number of electrons, complicating the connection to the computational variables of the Kohn-Sham one-electron orbitals. Only recently, the analytical expressions for the chemical potential, one of the key concepts, have been derived by Cohen, Mori-Sánchez, and Yang, based on the potential functional theory formalism. In the present work, we obtain the analytical expressions for the real-space linear response function using the coupled perturbed Kohn-Sham and generalized Kohn-Sham equations, and the Fukui functions using the previous analytical expressions for chemical potentials of Cohen, Mori-Sánchez, and Yang. The analytical expressions are exact within the given exchange-correlation functional. They are applicable to all commonly used approximate functionals, such as local density approximation (LDA), generalized gradient approximation (GGA), and hybrid functionals. The analytical expressions obtained here for Fukui function and linear response functions, along with that for the chemical potential by Cohen, Mori-Sánchez, and Yang, provide the rigorous and efficient evaluation of the key quantities in conceptual density functional theory within the computational framework of the Kohn-Sham and generalized Kohn-Sham approaches. Furthermore, the obtained analytical expressions for Fukui functions, in conjunction with the linearity condition of the ground state energy as a function of the fractional charges, also lead to new local conditions on the exact functionals, expressed in terms of the second-order functional derivatives. We implemented the expressions and demonstrate the efficacy with some atomic and molecular calculations, highlighting the importance of relaxation effects.

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Section: Introductionmentioning

confidence: 99%

Analytical evaluation of Fukui functions and real-space linear response function

Yang

Cohen

Proft

et al. 2012

The Journal of Chemical Physics

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“…However, the frontier electron theory has its own limitations. Sometimes, reactivity may be determined by strong electrostatic forces rather than by frontier orbitals, especially for reactions associated with an aromatic system . In regard to the above analysis, it can be concluded that the carbon atoms in the benzene ring are all reactive to be attacked by radicals.…”

Section: Resultsmentioning

confidence: 99%

Dimethyl Phthalate Degradation by UV/H₂O₂: Combination of Experimental Methods and Quantum Chemical Calculation

Feng

Guo

et al. 2015

CLEAN Soil Air Water

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Photochemical degradation of typical phthalate esters, as, e.g. dimethyl phthalate (DMP), in water by the UV/H2O2 process was investigated. The degradation rate of DMP was affected by several reaction factors, including initial DMP concentration, H2O2 concentration, UV light intensity, and coexisting cations and anions. The DMP degradation rate decreased with increasing initial DMP concentration. Carbonate ions significantly reduced the reaction rate by 70.2%, while the degradation rate was improved ten‐fold in the presence of ferric ions. The initial reaction mechanism and possible degradation products were investigated using density functional theory (DFT), including B3LYP and M062X hybrid functional. The addition of OH radicals (OH•) to the C4 position of the DMP ring is energetically favored for the initial reaction of DMP with OH•. Dimethyl 4‐hydroxyphthalate (DMP‐4OH) is one of the initial degradation intermediates. A possible reaction mechanism was also proposed based on GC/MS analysis and quantum chemical calculations. The formation of DMP‐4OH has been explained by quantum chemical calculations, which indicates the advantage and promising role of this method in the degradation mechanism analysis.

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“…The Fukui function was defined as follows: Where was electronic density, N was number of electrons and ν was external potential exerted by the nuclei. The concept was first described by Fukui in 1952 [93] and a corresponding definition with the Density functional theory (DFT) was given in 1984 [89, 91]. However, the condensed Fukui function was restricted to an atom within a molecule rather than a point in 3D space [94–98].…”

Section: Methodsmentioning

confidence: 99%

Predicting the Metabolic Sites by Flavin-Containing Monooxygenase on Drug Molecules Using SVM Classification on Computed Quantum Mechanics and Circular Fingerprints Molecular Descriptors

Chien-wei

Lin

2017

PLoS ONE

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As an important enzyme in Phase I drug metabolism, the flavin-containing monooxygenase (FMO) also metabolizes some xenobiotics with soft nucleophiles. The site of metabolism (SOM) on a molecule is the site where the metabolic reaction is exerted by an enzyme. Accurate prediction of SOMs on drug molecules will assist the search for drug leads during the optimization process. Here, some quantum mechanics features such as the condensed Fukui function and attributes from circular fingerprints (called Molprint2D) are computed and classified using the support vector machine (SVM) for predicting some potential SOMs on a series of drugs that can be metabolized by FMO enzymes. The condensed Fukui function fA− representing the nucleophilicity of central atom A and the attributes from circular fingerprints accounting the influence of neighbors on the central atom. The total number of FMO substrates and non-substrates collected in the study is 85 and they are equally divided into the training and test sets with each carrying roughly the same number of potential SOMs. However, only N-oxidation and S-oxidation features were considered in the prediction since the available C-oxidation data was scarce. In the training process, the LibSVM package of WEKA package and the option of 10-fold cross validation are employed. The prediction performance on the test set evaluated by accuracy, Matthews correlation coefficient and area under ROC curve computed are 0.829, 0.659, and 0.877 respectively. This work reveals that the SVM model built can accurately predict the potential SOMs for drug molecules that are metabolizable by the FMO enzymes.

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Perspective on "Density functional approach to the frontier-electron theory of chemical reactivity"

Cited by 422 publications

References 36 publications

Analytical evaluation of Fukui functions and real-space linear response function

Analytical evaluation of Fukui functions and real-space linear response function

Dimethyl Phthalate Degradation by UV/H₂O₂: Combination of Experimental Methods and Quantum Chemical Calculation

Predicting the Metabolic Sites by Flavin-Containing Monooxygenase on Drug Molecules Using SVM Classification on Computed Quantum Mechanics and Circular Fingerprints Molecular Descriptors

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Perspective on "Density functional approach to the frontier-electron theory of chemical reactivity"

Cited by 422 publications

References 36 publications

Analytical evaluation of Fukui functions and real-space linear response function

Analytical evaluation of Fukui functions and real-space linear response function

Dimethyl Phthalate Degradation by UV/H2O2: Combination of Experimental Methods and Quantum Chemical Calculation

Predicting the Metabolic Sites by Flavin-Containing Monooxygenase on Drug Molecules Using SVM Classification on Computed Quantum Mechanics and Circular Fingerprints Molecular Descriptors

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Dimethyl Phthalate Degradation by UV/H₂O₂: Combination of Experimental Methods and Quantum Chemical Calculation