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Issue 14, 2014
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Conceptual DFT: chemistry from the linear response function

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Abstract

Within the context of reactivity descriptors known in conceptual DFT, the linear response function (χ(r,r′)) remained nearly unexploited. Although well known, in its time dependent form, in the solid state physics and time-dependent DFT communities the study of the “chemistry” present in the kernel was, until recently, relatively unexplored. The evaluation of the linear response function as such and its study in the time independent form are highlighted in the present review. On the fundamental side, the focus is on the approaches of increasing complexity to compute and represent χ(r,r′), its visualisation going from plots of the unintegrated χ(r,r′) to an atom condensed matrix. The study on atoms reveals its physical significance, retrieving atomic shell structure, while the results on molecules illustrate that a variety of chemical concepts are retrieved: inductive and mesomeric effects, electron delocalisation, aromaticity and anti-aromaticity, σ and π aromaticity,…. The applications show that the chemistry of aliphatic (saturated and unsaturated) chains, saturated and aromatic/anti-aromatic rings, organic, inorganic or metallic in nature, can be retrieved via the linear response function, including the variation of the electronic structure of the reagents along a reaction path. The connection of the linear response function with the concept of nearsightedness and the alchemical derivatives is also highlighted.

Graphical abstract: Conceptual DFT: chemistry from the linear response function

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Article information


Submitted
11 Dec 2013
First published
17 Feb 2014

Chem. Soc. Rev., 2014,43, 4989-5008
Article type
Review Article

Conceptual DFT: chemistry from the linear response function

P. Geerlings, S. Fias, Z. Boisdenghien and F. De Proft, Chem. Soc. Rev., 2014, 43, 4989
DOI: 10.1039/C3CS60456J

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