Estimation of Effective Parameters for the Transition-Metal Complexes by Mapping Self-Interaction Correction onto GGA+U

2020-03-12T11:09:52Z (GMT) by Jae-Hyeon Parq
We propose a method to calculate the Hubbard U parameter in GGA+U or the α pa
rameter in the atomic self-interaction correction (ASIC) scheme for transition-metal
d orbitals by mapping the self-interaction correction (SIC) onto GGA+U, which is
suitable for atom-centered basis sets. SIC can offer a substitute for the Hubbard
U parameter in GGA+U, although its usage should be limited considering the dif
ferences between GGA+U and SIC. Approximations to reduce computational cost
for self-interaction (SI) corrected localized orbitals are deduced from the properties
of the unitary transformation in SIC and the atomic likeness of molecular orbitals
dominated by transition-metal d orbitals, and the parameters are obtained from the
approximate forms of the localized orbitals. First-row transition-metal complexes
were tested, and the results are comparable to experimental measurements and pre
vious calculations. Our method does not guarantee better results than those of
the linear response method or hybrid functionals, but mapping from SIC suppresses
overestimation of the U parameter to obtain proper geometries and energies for Fe
porphyrin-imidazole, Fe-porphyrin-CO and FeO2 modeling