Energy components in energy decomposition analysis (EDA) are path functions; why does it matter?

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Authors

ANDRADA Diego M. FOROUTANNEJAD Cina

Year of publication 2020
Type Article in Periodical
Magazine / Source Physical Chemistry Chemical Physics
MU Faculty or unit

Faculty of Science

Citation
Web https://doi.org/10.1039/D0CP04016A
Doi http://dx.doi.org/10.1039/d0cp04016a
Keywords energy decomposition analysis
Description Here, we discuss that unlike bond dissociation energy (BDE) that is a state function quantity, the energy components of the energy decomposition analysis (EDA), i.e. electrostatic interaction, Pauli repulsion, and orbital interaction, are path (process) function quantities. Being a path function means that EDA energy components are not uniquely defined, i.e. the relative magnitudes of the orbital interaction, Pauli repulsion, and electrostatic components may vary depending on the selected pathway for EDA. Therefore, at best, EDA can define whether closely related chemical bonds are more or less ionic/covalent compared with each other. However, a precise assessment of the nature of a certain type of chemical bond using EDA is a questionable task. Besides, we briefly discuss that the widely used EDA pathway, which is merely an arbitrary choice among infinite possible paths, comes to conclusions not consistent with our widely accepted knowledge of bond formation even for the simplest molecules.
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