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 - 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 -