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Theoretical prediction of g tensors and hyperfine coupling tensors of triplet molecules
Author(s) -
I'haya Y. J.,
Morikawa Tetsuo,
Nakano Junji
Publication year - 2009
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.560160823
Subject(s) - anisotropy , excited state , isotropy , delocalized electron , chemistry , hyperfine structure , triplet state , molecule , superposition principle , spin (aerodynamics) , molecular physics , atomic physics , physics , quantum mechanics , thermodynamics , organic chemistry
This is the first time that all‐valence‐electron SCF MO calculations of g tensors and hyperfine coupling (HFC) tensors of some triplet molecules have been carried out. The molecular orbital spin density is partitioned into the σ and π‐electron spin delocalization (SD) terms and the remaining terms of spin polarization (SP) which arise from the CI effect. The g tensors for CH 2 and some other carbenes which have ground triplet states and the excited triplet formaldehyde are evaluated. The origin of HFC in CH 2 is analyzed in detail by using the partitioning method for spin density matrices. The absolute values of the isotropic and anisotropic 13 C HFC tensors of CH 2 calculated by taking into account the SD terms only are in good agreement with those observed for CD 2 . The contribution of the SP terms to the isotropic HFC tensors is fairly large, while the contribution to the anisotropic HFC tensors is negligibly small.