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The Independent Gradient Model: a new approach for probing strong and weak interactions in molecules from wave function calculations

Abstract : Extracting the chemical interaction signature from local descriptors based on electron density (ED) is still a fruitful field of development in chemical interpretation. In a previous work using promolecular ED (frozen ED), the new descriptor was defined. It represents the difference between a virtual upper limit of the ED gradient (| ρ !"# |) representing a non-interacting system and the true ED gradient | |. It can be seen as a measure of electron sharing brought by ED contragradience. A compelling feature of this model is to provide an automatic workflow that extracts the signature of interactions between selected groups of atoms. As with the NCI (Non Covalent Interaction) approach, it provides chemists with a visual understanding of interactions present in chemical systems. | ρ !"# | is achieved simply by using absolute values upon summing the individual gradient contributions making up the total ED gradient. Hereby, we extend this model to relaxed ED calculated from a wave function. To this end, we formulate the Gradient-Based Partitioning (GBP) to assess the contribution of each orbital to the total ED gradient. We highlight these new possibilities across two prototypical examples of organic chemistry: the unconventional hexamethylbenzene dication involving a hexa-coordinated carbon atom and the b-thioaminoacrolein. It will be shown how a bond-bybond picture can be obtained from a wave function opening the way to monitor specific interactions along reaction paths.
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https://hal.univ-reims.fr/hal-03377532
Contributor : Eric Hénon Connect in order to contact the contributor
Submitted on : Thursday, October 14, 2021 - 11:12:11 AM
Last modification on : Friday, December 3, 2021 - 11:42:49 AM

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Corentin Lefebvre, Hassan Khartabil, Jean-Charles Boisson, Julia Contreras-García, Jean-Philip Piquemal, et al.. The Independent Gradient Model: a new approach for probing strong and weak interactions in molecules from wave function calculations. ChemPhysChem, Wiley-VCH Verlag, 2018, 19 (6), pp.724-735. ⟨10.1002/cphc.201701325⟩. ⟨hal-03377532⟩

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