Relativistic effects on the Fukui function

Sablon, Nick; Mastalerz, Remigius; De Proft, Frank; Geerlings, Paul; Reiher, Markus
October 2010
Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Oct2010, Vol. 127 Issue 3, p195
Academic Journal
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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