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Development of spin‐dependent relativistic open‐shell H artree– F ock theory with time‐reversal symmetry (I): The unrestricted approach
Author(s) -
Nakano Masahiko,
Seino Junji,
Nakai Hiromi
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25356
Subject(s) - physics , quaternion , symmetry (geometry) , spin (aerodynamics) , open shell , relativistic quantum chemistry , convergence (economics) , spin–orbit interaction , quantum mechanics , quantum electrodynamics , mathematics , geometry , economics , thermodynamics , economic growth
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.