The local response of global descriptors

Abstract

We consider the problem of defining an appropriate local descriptor corresponding to an arbitrary global descriptor. Although it does not seem easy to rigorously and uniquely define local analogues of derived global descriptors (e.g., the electrophilicity) or the fundamental global descriptors associated with the canonical ensemble (e.g., the hardness), the local response of these global descriptors can be defined unambiguously. We look at the local response of the global electrophilicity and compare it to the conventional, ad hoc, definition of the local electrophilicity. The local response of global nucleofugality and electrofugality is also discussed.

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Acknowledgements

PWA and FHZ wish to thank NSERC of Canada and Compute Canada for monetary and computing support. FHZ, SF, and TV thank the FWO of Belgium. TV thanks the Research Board of Ghent University (BOF). EVM thanks Nucleus Millennium CPC #120082 and Fondecyt #1160197.

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Correspondence to Paul W. Ayers.

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Published as part of the special collection of articles “Festschrift in honour of A. Vela”.

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Heidar-Zadeh, F., Fias, S., Vöhringer-Martinez, E. et al. The local response of global descriptors. Theor Chem Acc 136, 19 (2017). https://doi.org/10.1007/s00214-016-2036-0

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Keywords

  • Conceptual density functional theory
  • Electrophilicity
  • Local reactivity descriptor
  • Response function
  • Chemical reactivity indicator