Unmasking Static Correlation Error in Hybrid Kohn–Sham Density Functional Theory

To uncover the way Hartree–Fock exchange brings static correlation error into hybrid Kohn–Sham density functional theory, we compare the potential energy curves of four diatomic molecules, namely, H2, F2, HF, and NaF, using both restricted and unrestricted Kohn–Sham theory. We find that increasing t...

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Published inJournal of chemical theory and computation Vol. 16; no. 9; pp. 5432 - 5440
Main Authors Zhang, Dayou, Truhlar, Donald G
Format Journal Article
LanguageEnglish
Published Washington American Chemical Society 08.09.2020
Subjects
Chemical calculations
Correlation
Density functional theory
Diatomic molecules
Electron correlation
Energy
Errors
Exchanging
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Potential energy
Wave function
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Summary:To uncover the way Hartree–Fock exchange brings static correlation error into hybrid Kohn–Sham density functional theory, we compare the potential energy curves of four diatomic molecules, namely, H2, F2, HF, and NaF, using both restricted and unrestricted Kohn–Sham theory. We find that increasing the percentage of Hartree–Fock exchange significantly increases the static correlation error because Hartree–Fock exchange replaces the ability of local exchange in density functionals to account for the localization effects associated with static correlation.
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SC0008688; FG02-17ER16362
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
ISSN:1549-9618
1549-9626
1549-9626
DOI:10.1021/acs.jctc.0c00585