### Abstract

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.

Original language | English |
---|---|

Article number | 164104 |

Journal | Journal of Chemical Physics |

Volume | 150 |

Issue number | 16 |

DOIs | |

Publication status | Published - 2019 Apr 28 |

### Fingerprint

### ASJC Scopus subject areas

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry

### Cite this

*Journal of Chemical Physics*,

*150*(16), [164104]. https://doi.org/10.1063/1.5090523

**Extension and acceleration of relativistic density functional theory based on transformed density operator.** / Ikabata, Yasuhiro; Oyama, Takuro; Hayami, Masao; Seino, Junji; Nakai, Hiromi.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 150, no. 16, 164104. https://doi.org/10.1063/1.5090523

}

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

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.

UR - http://www.scopus.com/inward/record.url?scp=85064954887&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85064954887&partnerID=8YFLogxK

U2 - 10.1063/1.5090523

DO - 10.1063/1.5090523

M3 - Article

VL - 150

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 16

M1 - 164104

ER -