Examining the Impact of Local Condition Violations on Energy Computations in DFT
arXiv:2403.14073 · doi:10.1002/jcc.70005
Abstract
This work introduces Extent of Violation Indices (EVIs), a novel metric for quantifying how well exchange-correlation functionals adhere to local conditions. Applying EVIs to a diverse set of molecules for GGA functionals reveals widespread violations, particularly for semi-empirical functionals. We leverage EVIs to explore potential connections between these violations and errors in chemical properties. While no correlation is observed for atomization energies, a link emerges between EVIs and total energies. Similarly, the analysis of reaction energies suggests weak positive correlations for specific conditions, but definitive conclusions about error cancellation require advancements in both functional accuracy and our understanding of cancellation mechanisms. Overall, this study highlights EVIs as a powerful tool for analyzing functional behavior and adherence to local conditions, paving the way for future research to fully elucidate the impact of violations on energy errors.
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