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

Area of Science:

• Computational Chemistry
• Materials Science

Background:

• Density functional theory (DFT) is widely used for thermochemical property calculations.
• Accurate DFT calculations for halogen-containing compounds are crucial for electrochemistry and ionic effect research.

Purpose of the Study:

• To evaluate the accuracy of DFT for halogen thermochemistry.
• To develop and validate corrections for DFT errors in halogen species.

Main Methods:

• Assessed formation energies of various halogen species using six DFT functionals (GGA, meta-GGA, hybrid).
• Analyzed DFT errors in relation to species electronegativity and identified systematic trends.
• Devised and applied swift corrections to reduce DFT errors.

Main Results:

• DFT errors were found to correlate with the electronegativity of halogen species.
• Corrections significantly reduced mean absolute errors from 0.19 eV to 0.08 eV.
• Maximum absolute errors also decreased substantially, improving overall accuracy.

Conclusions:

• Developed corrections enhance DFT accuracy for halogen thermochemistry.
• Improved DFT calculations have a notable impact on predicting surface Pourbaix diagrams.
• The study provides a pathway for more reliable computational studies involving halogens.