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Journal Articles Journal of Chemical Theory and Computation Year : 2024

Exploring the Reactivity of Donor–Acceptor Systems through a Combined Conceptual and Constrained DFT Approach

Abstract

In the context of the conceptual Density Functional Theory (cDFT) and based on the computational efficiency of the constrained DFT (CDFT), we demonstrate that chemical reactivity can be governed by the difference between the local interacting chemical potentials of the reactants (referred as Edual), in agreement with the Sanderson's equalization principle. In a proof-of-concept study, we investigated illustrative examples involving typical non-covalent donor-acceptor systems as well as reactive systems are provided. For the selected systems, our approach reveals a significant mimicking between Edual and the DFT-computed intermolecular interaction energy profiles. We further evaluate the influence of the coulomb and exchange-correlation contributions in Edual. These latter results suggest that numerous potential energy surfaces of clusters can be explored using a Sanderson-like model only based classical interactions between molecular orbitals domains. To conclude, this study achieved a deeper understanding of the principles of cDFT and assessed, in a wider context, its efficiency in predicting the chemical reactivity.
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Avant la publication
Wednesday, August 14, 2024
Embargoed file
Wednesday, August 14, 2024
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Dates and versions

hal-04467008 , version 1 (19-02-2024)

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Johanna Klein, Julien Pilmé. Exploring the Reactivity of Donor–Acceptor Systems through a Combined Conceptual and Constrained DFT Approach. Journal of Chemical Theory and Computation, 2024, ⟨10.1021/acs.jctc.3c01248⟩. ⟨hal-04467008⟩
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