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Title: Non-empirical, low-cost recovery of exact conditions with model-Hamiltonian inspired expressions in jmDFT

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5091563· OSTI ID:1612843
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
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Density functional theory (DFT) is widely applied to both molecules and materials, but well known energetic delocalization and static correlation errors in practical exchange-correlation approximations limit quantitative accuracy. Common methods that correct energetic delocalization errors, such as the Hubbard U correction in DFT+U or Hartree-Fock exchange in global hybrids, do so at the cost of worsening static correlation errors. We recently introduced an alternate approach [Bajaj et al., J. Chem. Phys. 147, 191101 (2017)] known as judiciously modified DFT (jmDFT), wherein the deviation from exact behavior of semilocal functionals over both fractional spin and charge, i.e., the so-called flat plane, was used to motivate functional forms of second order analytic corrections. In this work, we introduce fully nonempirical expressions for all four coefficients in a DFT+U+J-inspired form of jmDFT, where all coefficients are obtained only from energies and eigenvalues of the integer-electron systems. We show good agreement for U and J coefficients obtained nonempirically as compared with the results of numerical fitting in a jmDFT U+J/J' correction. Incorporating the fully nonempirical jmDFT correction reduces and even eliminates the fractional spin error at the same time as eliminating the energetic delocalization error. We show that this approach extends beyond s-electron systems to higher angular momentum cases including p- and d-electrons. Finally, we diagnose some shortcomings of the current jmDFT approach that limit its ability to improve upon DFT results for cases such as weakly bound anions due to poor underlying semilocal functional behavior.

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0018096
OSTI ID:
1612843
Alternate ID(s):
OSTI ID: 1507619
Journal Information:
Journal of Chemical Physics, Vol. 150, Issue 15; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
Self consistent field methods
Density functional theory
Ions and properties
Chemical elements
Delocalization
Electronic structure methods