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Determination of spin‐orbit coupling contributions in the framework of density functional theory
Author(s) -
Chiodo Sandro,
Russo Nino
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20847
Subject(s) - density functional theory , coupling (piping) , singlet state , spin–orbit interaction , operator (biology) , basis (linear algebra) , orbit (dynamics) , pauli exclusion principle , hybrid functional , spin (aerodynamics) , physics , functional theory , quantum mechanics , computational physics , chemistry , mathematics , materials science , thermodynamics , excited state , biochemistry , geometry , repressor , transcription factor , engineering , metallurgy , gene , aerospace engineering
We present a noniterative method to calculate spin‐orbit coupling by means of a theoretical approach that provides the use of the full Breit–Pauli operator. This method was applied to compute one and two‐electron spin‐orbit coupling contributions between singlet and triplet, and doublet and doublet states, respectively. These states have been represented by monodeterminantal wave functions and optimized using the PW91 gradient‐corrected exchange‐correlation functional and the hybrid B3LYP one. They have been supplied by the conventional density functional theory packages, and thus coupled by our spin‐orbit coupling code. Different size basis sets have been employed and the obtained results have been compared with the corresponding ones provided by some of the already existing methods and with the experimental data. They have been found to be in good quantitative agreement. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008