Path dependency of Energy Decomposition Analysis:
Collective bonding as a corner case
Vojtěch Šádeka,b
, Cina Foroutan-Nejadc
a
CEITEC, Masaryk University, Kamenice 5, 62500 Brno
b
Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 62500, Brno
c
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw
e-mail: vojtech.sadek@gmail.com
Energy Decomposition Analysis (EDA) is a technique of computational chemistry for
classification of chemical bonds or interactions.
It partitionates bonding energy into meaningful components: preparation energy, electrostatic
interaction, Pauli repulsion and orbital interaction energy. The calculation consists of
squashing wavefunctions of relaxed fragments to the geometry of the molecule, followed by
antisymmetrization and relaxation. It has been demonstrated earlier that the components
depend on the choice of “reaction” path1,2
.
Alternative to EDA might be Quantum Theory of Atoms in Molecules (QTAIM) with
Interacting Quantum Atoms (IQA) method of partitioning of total energy and different
definition of interactions. According to this definition, the components are guaranteed to be
just a function of state since the calculation doesn’t depend on any construction.
Published results of my other project3
have been challenged by a competing team using
arguments involving EDA calculation in situations where it hit its limitations.
Our project on proper explanation of the limitations of EDA method
References
1. Solà, M., Duran, M. & Poater, J. “The energy components of the extended transition
state energy decomposition analysis are path functions: the case of water tetramer.”
Theor Chem Acc 140, 33 (2021). doi:10.1007/s00214-021-02730-3
2. Poater, J., Andrada, D. M., Solà, M. & Foroutan-Nejad, C. Path-dependency of energy
decomposition analysis & the elusive nature of bonding. Phys. Chem. Chem. Phys.
24, 2344–2348 (2022) doi:10.1039/D1CP04135E
3. Sowlati-Hashjin, S., Šadek, V., Sadjadi, S., Karttunen, M., Martín-Pendás, A.,
Foroutan-Nejad. C. "Collective interactions among organometallics are exotic bonds
hidden on lab shelves". Nat Commun 13, 2069 (2022).
doi:10.1038/s41467-022-29504-0
4. Šádek, V., Sowlati-Hashjin, S., Sadjadi, S., Karttunen, M., Martín-Pendás A.,
Foroutan-Nejad, C. Reply to “On the existence of collective interactions”, accepted by
Nat. Commun. temporarily doi:10.26434/chemrxiv-2023-9jv24