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Spin–Orbit Contributions in High‐Spin Nitrenes/Carbenes: A Hybrid CASSCF/MRMP2 Study of Zero‐Field Splitting Tensors
Author(s) -
Sugisaki Kenji,
Toyota Kazuo,
Sato Kazunobu,
Shiomi Daisuke,
Kitagawa Masahiro,
Takui Takeji
Publication year - 2010
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201000492
Subject(s) - zero field splitting , spin (aerodynamics) , tensor (intrinsic definition) , nitrene , delocalized electron , atomic orbital , chemistry , field (mathematics) , physics , condensed matter physics , computational chemistry , spin polarization , quantum mechanics , electron , thermodynamics , geometry , biochemistry , mathematics , pure mathematics , catalysis
Zero‐field splitting (ZFS) tensors ( D tensors) of organic high‐spin oligonitrenes/oligocarbenes up to spin‐septet are quantitatively determined on the basis of quantum chemical calculations. The spin–orbit contributions, D SO tensors are calculated in terms of a hybrid CASSCF/MRMP2 approach, which was recently proposed by us. The spin–spin counterparts, D SS tensors are computed based on McWeeny–Mizuno’s equation in conjunction with the RODFT spin densities. The present calculations show that more than 10 % of ZFS arises from spin–orbit interactions in the high‐spin nitrenes under study. Contributions of spin‐bearing site–site interactions are estimated with the aid of a semi‐empirical model for the D tensors and found to be ca. 5 % of the D SO tensor. The analysis of intermediate states reveal that the largest contributions to the calculated D SO tensors are attributed to intra‐site spin flip excitations and delocalized π and π* orbitals play an important role in the inter‐site spin–orbit interactions.