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Relativistic effects on the Fukui function

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Abstract

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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Acknowledgments

N.S. acknowledges the Research Foundation, Flanders (FWO) for a position as research assistant and a research stay at M. Reiher’s group at the ETH Zurich. F.D.P. and P.G. thank the Vrije Universiteit Brussel (VUB) and FWO for continuous support to their research group. R.M. and M.R. gratefully acknowledge financial support by the Swiss National Science Foundation SNF (project 200020-121870).

Note added in Proof

After having revised this paper we got aware of a recent paper that investigates relativistic effects on the Fukui function of gold clusters: De HS, Krishnamurty S, Pal S (2009) J Phys Chem C 113:7101–7106.

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Authors and Affiliations

  1. Eenheid Algemene Chemie, Vrije Universiteit Brussel, Pleinlaan 2, 1050, Brussels, Belgium

    Nick Sablon, Frank De Proft & Paul Geerlings

  2. Laboratorium für Physikalische Chemie, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093, Zurich, Switzerland

    Remigius Mastalerz & Markus Reiher

Authors
  1. Nick Sablon
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  2. Remigius Mastalerz
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  3. Frank De Proft
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  4. Paul Geerlings
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  5. Markus Reiher
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Correspondence to Nick Sablon or Markus Reiher.

Additional information

Dedicated to the memory of Professor Jürgen Hinze and published as part of the Hinze Memorial Issue.

N. Sablon: Aspirant of the Research Foundation-Flanders (aspirant van het Fonds Wetenschappelijk Onderzoek-Vlaanderen).

N. Sablon, F. De Proft, and P. Geerlings are members of the QCMM Ghent-Brussels Alliance Group.

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Sablon, N., Mastalerz, R., De Proft, F. et al. Relativistic effects on the Fukui function. Theor Chem Acc 127, 195–202 (2010). https://doi.org/10.1007/s00214-009-0722-x

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