Computing Fukui functions without differentiating with respect to electron number. I. Fundamentals

Ayers, Paul W.; Proft, Frank De; Borgoo, Alex; Geerlings, Pau̧l

doi:10.1063/1.2736697

Cited by 66 publications

(79 citation statements)

References 66 publications

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“…This is because of their proven reliability and their ease of use [3]; methods aiming at an immediate evaluation of the (functional) derivatives in Eq. 2 have been thought up [40][41][42][43][44], but are computationally more demanding than formulae 11 and 12.…”

Section: Methodology and Computational Detailsmentioning

confidence: 99%

Relativistic effects on the Fukui function

et al. 2010

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The extent of relativistic effects on the Fukui function, which describes local reactivity trends within conceptual density functional theory (DFT), and frontier orbital densities has been analysed on the basis of three benchmark molecules containing the heavy elements: Au, Pb, and Bi. Various approximate relativistic approaches have been tested and compared with the four-component fully relativistic reference. Scalar relativistic effects, as described by the scalar zeroth-order regular approximation methodology and effective core potential calculations, already provide a large part of the relativistic corrections. Inclusion of spin-orbit coupling effects improves the results, especially for the heavy p-block compounds. We thus expect that future conceptual DFT-based reactivity studies on heavy-element molecules can rely on one of the approximate relativistic methodologies.

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Section: Methodology and Computational Detailsmentioning

confidence: 99%

Relativistic effects on the Fukui function

et al. 2010

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“…42 The finite difference approximate is exact for exact computations ͑full configuration interaction͒, but is not exact for the computationally economical methods that are commonly used in conceptual DFT. 35,43 Another aspect of chemistry, besides reactivity, that has played a very prominent role during its development is the view that molecules consist of atoms held together by chemical bonds. Many aspects of chemical reactivity are often traced back to the atoms and the bonds that compose the molecule, as this language facilitates constructing predictive models that only require information about the composition of a reacting molecule.…”

Section: ͑2͒mentioning

confidence: 99%

Critical thoughts on computing atom condensed Fukui functions

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Alsenoy

et al. 2007

The Journal of Chemical Physics

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Different procedures to obtain atom condensed Fukui functions are described. It is shown how the resulting values may differ depending on the exact approach to atom condensed Fukui functions. The condensed Fukui function can be computed using either the fragment of molecular response approach or the response of molecular fragment approach. The two approaches are nonequivalent; only the latter approach corresponds in general with a population difference expression. The Mulliken approach does not depend on the approach taken but has some computational drawbacks.The different resulting expressions are tested for a wide set of molecules. In practice one must make seemingly arbitrary choices about how to compute condensed Fukui functions, which suggests questioning the role of these indicators in conceptual density-functional theory.

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“…This approximation is exact for exact calculations (full CI), and a good approach in the computationally economic methods commonly used in conceptual DFT [20,21,22]. This interpolation uses the electron densities of the atoms at integer populations, which are available through atomic calculations.…”

Section: Iterative Hirshfeld Methodsmentioning

confidence: 99%

A self‐consistent Hirshfeld method for the atom in the molecule based on minimization of information loss

et al. 2011

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Based on the so-called Hirshfeld atom in the molecule (AIM) scheme, a new AIM method is presented. The method is similar to the Hirshfeld-I scheme, with the AIM weight function being constructed by minimizing the information loss upon formation of the molecule, but now requiring explicitly that the promolecular densities integrate to the same number of electrons as the AIM densities. This new weight function leads to a new iterative AIM scheme, and the resulting operative scheme is examined and discussed. The final results indicate that the newly proposed method does not perform as well as the Hirshfeld-I method.

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Computing Fukui functions without differentiating with respect to electron number. I. Fundamentals

Cited by 66 publications

References 66 publications

Relativistic effects on the Fukui function

Relativistic effects on the Fukui function

Critical thoughts on computing atom condensed Fukui functions

A self‐consistent Hirshfeld method for the atom in the molecule based on minimization of information loss

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