Decoding Energy Decomposition Analysis: Machine-Learned Insights on the Impact of the Density Functional on the Bonding Analysis

TL;DR

This study investigates how the choice of density functional influences energy decomposition analysis of chemical bonds, revealing that different functionals cause significant variation but have minimal impact on bonding interpretation.

Contribution

It introduces a comprehensive analysis of the effect of various density functionals on EDA, combining data-driven methods to assess their influence on bonding interpretation.

Findings

Significant variation among functionals in EDA terms, especially dispersion corrections.

Unsupervised learning reveals minimal impact of functional choice on bonding interpretation.

Dispersion correction terms show the highest variability across functionals.

Abstract

The concept of chemical bonding is a crucial aspect of chemistry that aids in understanding the complexity and reactivity of molecules and materials. However, the interpretation of chemical bonds can be hindered by the choice of the theoretical approach and the specific method utilized. This study aims to investigate the effect of choosing different density functionals on the interpretation of bonding achieved through energy decomposition analysis (EDA). To achieve this goal, a data set was created, representing four bonding groups and various combinations of functionals and dispersion correction schemes. The calculations showed significant variation among the different functionals for the EDA terms, with the dispersion correction terms exhibiting the highest variability. More information was extracted by using unsupervised learning in combination with dimensionality reduction on the data set. Results indicate that, despite the differences in the EDA terms obtained from different functionals, the functional has the least significant impact, suggesting minimal influence on the bonding interpretation.