Calculation of Fukui Functions Without Differentiating to the Number of Electrons. 3. Local Fukui Function and Dual Descriptor

Fievez, Tim; Sablon, Nick; Proft, Frank De; Ayers, Paul W.; Geerlings, Pau̧l

doi:10.1021/ct800027e

Cited by 52 publications

(38 citation statements)

References 54 publications

(105 reference statements)

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“…[39,[47][48][49] Based on our results, we only expect them to work properly for activated ring systems, a conclusion similar to previous studies on the S E Ar reaction using conceptual DFT indices. [46,[50][51][52] Likewise, the weakness of the one-reactant approach is unmistakably illustrated. Future reactivity indices, should therefore not only focus on the orbital/electrostatic interaction, but mix both terms and properly take into account the effect of the attacking electrophile.…”

Section: Discussionmentioning

confidence: 99%

Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials

et al. 2011

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The S E Ar reaction was scrutinized using a quantitative, fragment-based interaction energy decomposition analysis (EDA) as implemented in the ADF program. The interaction energy between monosubstituted benzene derivatives and a model electrophile at the onset of the reaction was studied and decomposed into Pauli repulsion, electrostatic interaction and orbital interaction terms for a plane parallel to the

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Section: Discussionmentioning

confidence: 99%

Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials

et al. 2011

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“…The matching criteria based on the Fukui function could be problematic in cases where it is difficult to determine the net direction of charge transfer between the reactants, or when there are several reacting centers on each molecule that can exchange electrons among them. As a way to circumvent these problems, recent regio‐selectivity studies in c‐DFT make use of the dual descriptor:

Δ f (r) = {(\frac{δ η}{δ ν false(boldr false)})}_{N} = {(\frac{\partial f false(boldr false)}{\partial N})}_{ν false(boldr false)} ≅ f {false(boldr false)}^{+} - f {false(boldr false)}^{-}

…”

Section: Conceptual Dft Descriptorsmentioning

confidence: 99%

Geometrical distortions and charge transfer in munchnöne regio‐selectivity: A conceptual density functional study

González

Hernández‐Castillo

Montero‐Cabrera

et al. 2017

Int J of Quantum Chemistry

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Dipolar cycloaddition reactions involving munchnönes and simple dipolarophiles provide a versatile synthetic route toward pyrrole derivatives. However, despite their widespread use, there are still debates regarding the factors governing the regio‐selectivity of these reactions. In this contribution, we study the regio‐selectivity of 1,3‐dipolar cycloadditions of munchnönes and alkenes, and the ability of conceptual density functional theory (c‐DFT) descriptors to correctly study these processes. We base our analysis on the variation of different reactivity descriptors along the reaction path, calculated for the whole reacting complex, and for the isolated species, with the strained geometries they present within this supra‐molecular aggregate. The study of several global descriptors indicates that the path leading to the preferred product proceeds via an asynchronous mechanism, with the maximum extent of charge transfer occurring after the transition state. This helps to understand why several reactivity principles fail to correctly account for the position of the transition state in this case. This also explains why local c‐DFT descriptors fail to predict the observed majoritarian regio‐isomer. These results highlight the fundamental role of the distortion effects for determining the extent of charge transfer between the reactants, and thus their impact on the reactivity and regio‐selectivity in these reactions.

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“…They appear in a mixed second-or higher order energy derivatives in which, using a Maxwell relation, the d/dN type problems were circumvented by writing the Fukui function as the functional derivative of the electronic chemical potential and the dual descriptor as the functional derivative of the hardness. [52][53][54] To sum up, a systematic, internally consistent, analytical procedure for the evaluation of the reactivity descriptors cited above is still lacking. Their numerical evaluation on the basis of a finite difference-type approach is not elegant and less insightful.…”

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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Calculation of Fukui Functions Without Differentiating to the Number of Electrons. 3. Local Fukui Function and Dual Descriptor

Cited by 52 publications

References 54 publications

Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials

Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials

Geometrical distortions and charge transfer in munchnöne regio‐selectivity: A conceptual density functional study

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

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