Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012)], which is based on the locality of relativistic effects, has been extended to a four-component Dirac-Coulomb Hamiltonian. In the previous study, the LUT scheme was applied only to a one-particle IODKH Hamiltonian with non-relativistic two-electron Coulomb interaction, termed IODKHC. The current study extends the LUT scheme to a two-particle IODKH Hamiltonian as well as one-particle one, termed IODKHIODKH, which has been a real bottleneck in numerical calculation. The LUT scheme with the IODKHIODKH Hamiltonian was numerically assessed in the diatomic molecules HX and X 2 and hydrogen halide molecules, (HX) n (X F, Cl, Br, and I). The total Hartree-Fock energies calculated by the LUT method agree well with conventional IODKHIODKH results. The computational cost of the LUT method is reduced drastically compared with that of the conventional method. In addition, the LUT method achieves linear-scaling with respect to the system size and a small prefactor.

Original languageEnglish
Article number144101
JournalJournal of Chemical Physics
Volume137
Issue number14
DOIs
Publication statusPublished - 2012 Oct 14

Fingerprint

Hamiltonians
Coulomb interactions
Electrons
electrons
interactions
Molecules
Hydrogen
relativistic effects
diatomic molecules
halides
Costs
costs
scaling
hydrogen

ASJC Scopus subject areas

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

Cite this

@article{b8d6f6252b624fe1bcd714c3cc7e5c7c,
title = "Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction",
abstract = "The local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012)], which is based on the locality of relativistic effects, has been extended to a four-component Dirac-Coulomb Hamiltonian. In the previous study, the LUT scheme was applied only to a one-particle IODKH Hamiltonian with non-relativistic two-electron Coulomb interaction, termed IODKHC. The current study extends the LUT scheme to a two-particle IODKH Hamiltonian as well as one-particle one, termed IODKHIODKH, which has been a real bottleneck in numerical calculation. The LUT scheme with the IODKHIODKH Hamiltonian was numerically assessed in the diatomic molecules HX and X 2 and hydrogen halide molecules, (HX) n (X F, Cl, Br, and I). The total Hartree-Fock energies calculated by the LUT method agree well with conventional IODKHIODKH results. The computational cost of the LUT method is reduced drastically compared with that of the conventional method. In addition, the LUT method achieves linear-scaling with respect to the system size and a small prefactor.",
author = "Junji Seino and Hiromi Nakai",
year = "2012",
month = "10",
day = "14",
doi = "10.1063/1.4757263",
language = "English",
volume = "137",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "14",

}

TY - JOUR

T1 - Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction

AU - Seino, Junji

AU - Nakai, Hiromi

PY - 2012/10/14

Y1 - 2012/10/14

N2 - The local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012)], which is based on the locality of relativistic effects, has been extended to a four-component Dirac-Coulomb Hamiltonian. In the previous study, the LUT scheme was applied only to a one-particle IODKH Hamiltonian with non-relativistic two-electron Coulomb interaction, termed IODKHC. The current study extends the LUT scheme to a two-particle IODKH Hamiltonian as well as one-particle one, termed IODKHIODKH, which has been a real bottleneck in numerical calculation. The LUT scheme with the IODKHIODKH Hamiltonian was numerically assessed in the diatomic molecules HX and X 2 and hydrogen halide molecules, (HX) n (X F, Cl, Br, and I). The total Hartree-Fock energies calculated by the LUT method agree well with conventional IODKHIODKH results. The computational cost of the LUT method is reduced drastically compared with that of the conventional method. In addition, the LUT method achieves linear-scaling with respect to the system size and a small prefactor.

AB - The local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012)], which is based on the locality of relativistic effects, has been extended to a four-component Dirac-Coulomb Hamiltonian. In the previous study, the LUT scheme was applied only to a one-particle IODKH Hamiltonian with non-relativistic two-electron Coulomb interaction, termed IODKHC. The current study extends the LUT scheme to a two-particle IODKH Hamiltonian as well as one-particle one, termed IODKHIODKH, which has been a real bottleneck in numerical calculation. The LUT scheme with the IODKHIODKH Hamiltonian was numerically assessed in the diatomic molecules HX and X 2 and hydrogen halide molecules, (HX) n (X F, Cl, Br, and I). The total Hartree-Fock energies calculated by the LUT method agree well with conventional IODKHIODKH results. The computational cost of the LUT method is reduced drastically compared with that of the conventional method. In addition, the LUT method achieves linear-scaling with respect to the system size and a small prefactor.

UR - http://www.scopus.com/inward/record.url?scp=84867560415&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84867560415&partnerID=8YFLogxK

U2 - 10.1063/1.4757263

DO - 10.1063/1.4757263

M3 - Article

VL - 137

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 14

M1 - 144101

ER -