TY - JOUR
T1 - Electronic structure of mononuclear Cu-based molecule from density-functional theory with self-interaction correction
AU - Karanovich, Anri
AU - Yamamoto, Yoh
AU - Jackson, Koblar Alan
AU - Park, Kyungwha
N1 - Funding Information:
Science Foundation under Grant No. ACI-1548562. We are grateful to Mark Pederson, Tunna Baruah, and Rajendra Zope for their extensive help in using and troubleshooting the FLOSIC code. We are also grateful to Kai Trepte for the discussion and for providing us with the frozen-density loop functionality and the fodMC code, and we thank Aleksander Wysocki for helping us set up the CASSCF calculation.
Funding Information:
This work was funded by the Department of Energy Basic Energy Sciences under Grant Nos. DE-SC0019033 and DE-SC0018331. The computational support was provided by the Virginia Tech Advanced Research Computing and the Extreme Science and Engineering Discovery Environment (XSEDE) under Project No. DMR060009N, which was supported by the National
Publisher Copyright:
© 2021 Author(s).
PY - 2021/7/7
Y1 - 2021/7/7
N2 - We investigate the electronic structure of a planar mononuclear Cu-based molecule [Cu(C6H4S2)2]z in two oxidation states (z = −2, −1) using density-functional theory (DFT) with Fermi-Löwdin orbital (FLO) self-interaction correction (SIC). The dianionic Cu-based molecule was proposed to be a promising qubit candidate. Self-interaction error within approximate DFT functionals renders severe delocalization of electron and spin densities arising from 3d orbitals. The FLO-SIC method relies on optimization of Fermi-Löwdin orbital descriptors (FODs) with which localized occupied orbitals are constructed to create SIC potentials. Starting with many initial sets of FODs, we employ a frozen-density loop algorithm within the FLO-SIC method to study the Cu-based molecule. We find that the electronic structure of the molecule remains unchanged despite somewhat different final FOD configurations. In the dianionic state (spin S = 1/2), FLO-SIC spin density originates from the Cu d and S p orbitals with an approximate ratio of 2:1, in quantitative agreement with multireference calculations, while in the case of SIC-free DFT, the orbital ratio is reversed. Overall, FLO-SIC lowers the energies of the occupied orbitals and, in particular, the 3d orbitals unhybridized with the ligands significantly, which substantially increases the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) compared to SIC-free DFT results. The FLO-SIC HOMO-LUMO gap of the dianionic state is larger than that of the monoanionic state, which is consistent with experiment. Our results suggest a positive outlook of the FLO-SIC method in the description of magnetic exchange coupling within 3d-element-based systems.
AB - We investigate the electronic structure of a planar mononuclear Cu-based molecule [Cu(C6H4S2)2]z in two oxidation states (z = −2, −1) using density-functional theory (DFT) with Fermi-Löwdin orbital (FLO) self-interaction correction (SIC). The dianionic Cu-based molecule was proposed to be a promising qubit candidate. Self-interaction error within approximate DFT functionals renders severe delocalization of electron and spin densities arising from 3d orbitals. The FLO-SIC method relies on optimization of Fermi-Löwdin orbital descriptors (FODs) with which localized occupied orbitals are constructed to create SIC potentials. Starting with many initial sets of FODs, we employ a frozen-density loop algorithm within the FLO-SIC method to study the Cu-based molecule. We find that the electronic structure of the molecule remains unchanged despite somewhat different final FOD configurations. In the dianionic state (spin S = 1/2), FLO-SIC spin density originates from the Cu d and S p orbitals with an approximate ratio of 2:1, in quantitative agreement with multireference calculations, while in the case of SIC-free DFT, the orbital ratio is reversed. Overall, FLO-SIC lowers the energies of the occupied orbitals and, in particular, the 3d orbitals unhybridized with the ligands significantly, which substantially increases the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) compared to SIC-free DFT results. The FLO-SIC HOMO-LUMO gap of the dianionic state is larger than that of the monoanionic state, which is consistent with experiment. Our results suggest a positive outlook of the FLO-SIC method in the description of magnetic exchange coupling within 3d-element-based systems.
UR - http://www.scopus.com/inward/record.url?scp=85109208856&partnerID=8YFLogxK
U2 - 10.1063/5.0054439
DO - 10.1063/5.0054439
M3 - Article
AN - SCOPUS:85109208856
VL - 155
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 1
M1 - 014106
ER -