Development of spin-dependent relativistic open-shell Hartree-Fock theory with time-reversal symmetry (I): The unrestricted approach

作者：Nakano Masahiko; Seino Junji; Nakai Hiromi^*

来源：International Journal of Quantum Chemistry, 2017, 117(10): e25356.

DOI：10.1002/qua.25356

• Kramers-unrestricted Hartree-Fock method
• open-shell system
• spin-dependent two-component relativistic calculation
• time-reversal symmetry

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.

• 出版日期2017-5-15