Inorganic Chemistry

Path-Dependency of Energy Decomposition Analysis & the Elusive Nature of Bonding

Authors

  • Jordi Poater Departament de Química Inorgànica i Orgànica and IQTCUB, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Catalonia, Spain ,
  • Diego M. Andrada Faculty of Natural Sciences and Technology, Department of Chemistry, Saarland University, 66123 Saarbrücken, Federal Republic of Germany ,
  • Miquel Sola Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, C/ Maria Aurèlia Capmany 69, 17003 Girona, Catalonia, Spain ,
  • Cina Foroutan-Nejad Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka44/52, 01-224, Warsaw, Poland

Abstract

Here, we provide evidence of the path-dependency of the energy components of the energy decomposition analysis scheme, EDA, by studying a set of thirty-one closed-shell model systems with D2h symmetry point group. For each system, we computed EDA components from nine different pathways and numerically showed that the relative magnitudes of the components differ substantially from one path to the other. Not surprisingly, yet unfortunately, the most significant variations in the relative magnitudes of the EDA components appear in the case of species with bonds within the grey zone of covalency and ionicity. We further discussed that the role of anions and their effect on arbitrary Pauli repulsion energy components affects the nature of bonding defined by EDA. The outcome variation by the selected partitioning scheme of EDA might bring arbitrariness when a careful comparison is overlooked.

Content

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Supplementary material

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Path-Dependency of Energy Decomposition Analysis & the Elusive Nature of Bonding
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