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
N1 - Funding Information:
Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, National Institutes of Natural Sciences (NINS). This study was supported in part by a grant-in-aid for Challenging Exploratory Research (KAKENHI 22655008) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan; by the Strategic Program for Innovative Research (SPIRE) from MEXT; by the Computational Materials Science Initiative (CMSI) from MEXT; and by a project research grant for “Practical in silico chemistry for material design” from the Research Institute for Science and Engineering (RISE), Waseda University. One of the authors (J.S.) is indebted to the Japan Society for the Promotion of Science (JSPS) for a Research Fellowship.
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.
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U2 - 10.1063/1.4757263
DO - 10.1063/1.4757263
M3 - Article
C2 - 23061833
AN - SCOPUS:84867560415
SN - 0021-9606
VL - 137
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 14
M1 - 144101
ER -