TY - JOUR
T1 - Unmasking Static Correlation Error in Hybrid Kohn-Sham Density Functional Theory
AU - Zhang, Dayou
AU - Truhlar, Donald G.
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/9/8
Y1 - 2020/9/8
N2 - 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.
AB - 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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U2 - 10.1021/acs.jctc.0c00585
DO - 10.1021/acs.jctc.0c00585
M3 - Article
C2 - 32693604
AN - SCOPUS:85090506198
SN - 1549-9618
VL - 16
SP - 5432
EP - 5440
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 9
ER -