Halogen Thermochemistry Assessed with Density Functional Theory: Systematic Errors, Swift Corrections and Effects on Electrochemistry.

ABSTRACT: Despite its sizable errors, density functional theory (DFT) is extensively used to evaluate thermochemical properties of gases, liquids and their interfaces with solids. As numerous halogen-containing compounds appear as reactants, products and/or electrolytes in electrochemical reactions, and ionic effects are currently an active area of research, it is important to evaluate the accuracy of DFT for halogen thermochemistry. Herein, we assess the formation energies of interhalogens, hydrogen halides, diatomic and atomic halogens and their ions using six widespread functionals at the GGA, meta-GGA and hybrid levels. We observe that DFT errors with respect to experiments are correlated with the electronegativity of the species and there are systematic trends across functionals, such that swif

SUBMITTER: Zapata JF 

PROVIDER: S-EPMC11997928 | biostudies-literature | 2025 Apr

REPOSITORIES: biostudies-literature