Stepwise Energy Decomposition Analysis:
Calculation with simple molecules
using modified GAMESS code
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
Bonding energy characterizes chemical bonds and other interatomic interactions.
Compuational chemistry provides several methods of interaction characterization. Energy
Decomposition Analysis (EDA) partionates bonding energy into components: preparation
energy, electrostatic interaction, Pauli repulsion and orbital interaction energy. The
caclulation consists of squashing wavefunctions of relaxed fragments to the geometry of the
molecule, followed by antisymetrization and relaxaton.
Sola and Poater demonstrated different results for different orders of composition for
multi-component structures.
Our aim is to demonstrate the limitations of the EDA method on supersimple diatomic
molecules. The plan was to split the calculation into several steps instead of just one. We
preyed on the source code availability of computational software GAMESS. The tweaked
code can perform the stepwise EDA. Results with H2, Li2. LiF, LiCl, N2 are shown.
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