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Vacancy‐Induced Deformation in a CoFe Prussian Blue Analogue – A Theoretical Investigation
Author(s) -
Krah Tim,
Suaud Nicolas,
Zanchet Alexandre,
Robert Vincent,
Ben Amor Nadia
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200857
Subject(s) - prussian blue , chemistry , cyanide , vacancy defect , ion , crystallography , alkali metal , molecule , cluster (spacecraft) , atomic orbital , inorganic chemistry , computational chemistry , chemical physics , electron , electrochemistry , organic chemistry , electrode , computer science , programming language , physics , quantum mechanics
The impact of the number and positions of Rb ions in the RbCo[Fe(CN) 6 ] Prussian blue analogue is analyzed by means of complete active space self‐consistent field (CASSCF) and subsequent second‐order perturbation theory (CASPT2) calculations performed upon embedded cluster models. It is shown that the geometries and corresponding electronic structures of the monomeric [Co III (NC) 5 (OH 2 )] 2– and [Co II (NC) 5 (OH 2 )] 3– units are differently affected when the apical cyanide ligand is substituted by a water molecule. The Co III ion moves away from the equatorial plane by ca. 0.15 Å, whereas the Co II is almost not sensitive to the environmental change. Furthermore, we find that this phenomenon is rather independent of the positions and numbers of the nearest‐neighbour alkali ions. The Co ion displacement directly controls the overlap between the bridging cyanide and metal ion orbitals, a scenario which might be favorable to trigger electron transfer in the photomagnetic dimeric CoFe units of the CoFe Prussian blue analogues.