Examining the Impact of Local Constraint Violations on Energy Computations in DFT.

ABSTRACT: This work examines the impact of locally imposed constraints in Density Functional Theory (DFT). Using a metric referred to as the extent of violation index (EVI), we quantify how well exchange-correlation functionals adhere to local constraints. Applying EVIs to a diverse set of molecules for GGA functionals reveals constraint 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 significant statistical correlation emerges between EVIs and total energies. Similarly, the analysis of reaction energies suggests weak positive correlations for specific constraints. However, definitive conclusions about error cancellation m

SUBMITTER: Khanna V 

PROVIDER: S-EPMC11694564 | biostudies-literature | 2025 Jan

REPOSITORIES: biostudies-literature