TY - JOUR
T1 - Development of spin-dependent relativistic open-shell Hartree–Fock theory with time-reversal symmetry (I)
T2 - The unrestricted approach
AU - Nakano, Masahiko
AU - Seino, Junji
AU - Nakai, Hiromi
N1 - Funding Information:
The authors thank Prof. Wenjian Liu for helpful comments on KUHF and Dr. Inkoo Kim for technical advices on the quaternion calculations. Some of the present calculations were performed at the Research Center for Computational Science (RCCS), the Okazaki Research Facilities, and the National Institutes of Natural Sciences (NINS). This study was supported in part by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) program ‘Elements Strategy Initiative to Form Core Research Center’ (since 2012), and by the Core Research for Evolutional Science and Technology (CREST) Program ‘Theoretical Design of Materials with Innovative Functions Based on Relativistic Electronic Theory’ of the Japan Science and Technology Agency (JST). M.N. is grateful to the Early Bird Program from Waseda Research Institute for Science and Engineering for a Research Grant for Young Scientists.
Publisher Copyright:
© 2017 Wiley Periodicals, Inc.
PY - 2017/5/15
Y1 - 2017/5/15
N2 - An open-shell Hartree–Fock (HF) theory for spin-dependent, two-component relativistic calculations, termed the Kramers-unrestricted HF (KUHF) method, is developed. The present KUHF method, which is formulated as a relativistic counterpart of nonrelativistic UHF, is based on quaternion algebra and partly uses time-reversal symmetry. The fundamental characteristics of KUHF are discussed in this study. From numerical assessments, it was revealed that KUHF gives a corresponding solution to nonrelativistic UHF; furthermore, KUHF properly describes spin-orbit interactions. In addition, KUHF can improve the self-consistent field convergence behavior in spin-dependent calculations, for example, for f-block elements.
AB - An open-shell Hartree–Fock (HF) theory for spin-dependent, two-component relativistic calculations, termed the Kramers-unrestricted HF (KUHF) method, is developed. The present KUHF method, which is formulated as a relativistic counterpart of nonrelativistic UHF, is based on quaternion algebra and partly uses time-reversal symmetry. The fundamental characteristics of KUHF are discussed in this study. From numerical assessments, it was revealed that KUHF gives a corresponding solution to nonrelativistic UHF; furthermore, KUHF properly describes spin-orbit interactions. In addition, KUHF can improve the self-consistent field convergence behavior in spin-dependent calculations, for example, for f-block elements.
KW - Kramers-unrestricted Hartree–Fock method
KW - open-shell system
KW - spin-dependent two-component relativistic calculation
KW - time-reversal symmetry
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U2 - 10.1002/qua.25356
DO - 10.1002/qua.25356
M3 - Article
AN - SCOPUS:85012907677
SN - 0020-7608
VL - 117
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 10
M1 - e25356
ER -