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DOE OSTI · 1712685

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

Zhang, Dayou·Truhlar, Donald G.
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Abstract

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, H 2 , F 2 , HF, and NaF, using both restricted and unrestricted Kohn–Sham theory. Here, 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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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYChemical calculationsElectron correlationEnergyPotential energyWave function

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Zhang, Dayou, Truhlar, Donald G.. 2020-07-21. Unmasking Static Correlation Error in Hybrid Kohn–Sham Density Functional Theory. https://doi.org/10.1021/acs.jctc.0c00585

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