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

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States); University of Minnesota
  2. Univ. of Minnesota, Minneapolis, MN (United States)
+ Show Author Affiliations
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. 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.
Research Organization:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0008688
OSTI ID:
1712685
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 9 Vol. 16; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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