TY - JOUR

T1 - Extension and acceleration of relativistic density functional theory based on transformed density operator

AU - Ikabata, Yasuhiro

AU - Oyama, Takuro

AU - Hayami, Masao

AU - Seino, Junji

AU - Nakai, Hiromi

N1 - Funding Information:
Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, and Institutes of Natural Sciences (NINS). This study was supported by the CREST program “Creation of Innovative Functions of Intelligent Materials on the Basis of Element Strategy” of the Japan Science and Technology Agency (JST) and KAKENHI Grant No. JP18K14184 from the Japan Society for the Promotion of Science (JSPS).
Publisher Copyright:
© 2019 Author(s).

PY - 2019/4/28

Y1 - 2019/4/28

N2 - We report an extension of relativistic density functional theory (RDFT) within one-component or two-component expressions that relies on a unitary-transformed density operator as well as a unitary-transformed Hamiltonian [Oyama et al., Chem. Phys. Lett. 680, 37 (2017)]. The transformed density operator is introduced to avoid the picture-change effect in the electron density, density gradient, kinetic energy density, and exchange-correlation potential. We confirmed that the implementation based on the spin-free infinite-order Douglas-Kroll-Hess method gives total, orbital, and excitation energies close to the reference values given by four-component RDFT calculations. To reduce the computational cost due to the transformed density operator, the local unitary transformation was also implemented. Numerical assessments revealed that the present scheme enabled the RDFT calculation of polyatomic systems with negligibly small picture-change effect.

AB - We report an extension of relativistic density functional theory (RDFT) within one-component or two-component expressions that relies on a unitary-transformed density operator as well as a unitary-transformed Hamiltonian [Oyama et al., Chem. Phys. Lett. 680, 37 (2017)]. The transformed density operator is introduced to avoid the picture-change effect in the electron density, density gradient, kinetic energy density, and exchange-correlation potential. We confirmed that the implementation based on the spin-free infinite-order Douglas-Kroll-Hess method gives total, orbital, and excitation energies close to the reference values given by four-component RDFT calculations. To reduce the computational cost due to the transformed density operator, the local unitary transformation was also implemented. Numerical assessments revealed that the present scheme enabled the RDFT calculation of polyatomic systems with negligibly small picture-change effect.

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U2 - 10.1063/1.5090523

DO - 10.1063/1.5090523

M3 - Article

C2 - 31042880

AN - SCOPUS:85064954887

SN - 0021-9606

VL - 150

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 16

M1 - 164104

ER -