Development of spin‐dependent relativistic open‐shell Hartree–Fock theory with time‐reversal symmetry (I): The unrestricted approach |
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| Authors: | Masahiko Nakano Junji Seino Hiromi Nakai |
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| Affiliation: | 1. Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Tokyo, Japan;2. Research Institute for Science and Engineering, Waseda University, Tokyo, Japan;3. CREST, Japan Science and Technology Agency, Kawaguchi, Saitama, Japan;4. ESICB, Kyoto University, Kyoto, Japan |
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| Abstract: | 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. |
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| Keywords: | Kramers‐unrestricted Hartree– Fock method open‐shell system spin‐dependent two‐component relativistic calculation time‐reversal symmetry |
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