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Study of the Light‐Induced Spin Crossover Process of the [Fe II (bpy) 3 ] 2+ Complex
Author(s) -
de Graaf Coen,
Sousa Carmen
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200903423
Subject(s) - singlet state , excited state , spin states , excitation , spin crossover , atomic physics , triplet state , spin (aerodynamics) , ligand field theory , ab initio , molecular physics , chemistry , materials science , photochemistry , physics , crystallography , ion , organic chemistry , quantum mechanics , thermodynamics
Ab initio calculations have been performed on [Fe II (bpy) 3 ] 2+ (bpy=bipyridine) to establish the variation of the energy of the electronic states relevant to light‐induced excited‐state spin trapping as a function of the Feligand distance. Light‐induced spin crossover takes place after excitation into the singlet metal‐to‐ligand charge‐transfer (MLCT) band. We found that the corresponding electronic states have their energy minimum in the same region as the low‐spin (LS) state and that the energy dependence of the triplet MLCT states are nearly identical to the 1 MLCT states. The high‐spin (HS) state is found to cross the MLCT band near the equilibrium geometry of the MLCT states. These findings give additional support to the hypothesis of a fast singlet–triplet interconversion in the MLCT manifold, followed by a 3 MLCT–HS ( 5 T 2 ) conversion accompanied by an elongation of the FeN distance.