Abstract
The 57Fe electron contact densities and the corresponding Mössbauer isomer shifts of RbMn[Fe(CN)6]·H2O are calculated with the use of ab initio wavefunction methods and double hybrid density functional method. The theoretical analysis of possible origin of the two slightly different signals in the Mössbauer spectra observed at 293 K and 50 K (Vertelman et al. 2008 Chem. Mater. 20 1236-38) is carried out. The measured differences of 0.083 – 0.105 mm/s between the high-temperature and low-temperature phases can be attributed to the different oxidation states of iron: the iron is in FeIII oxidation state in the high temperature phase and FeII state in the low temperature phase. The smaller isomer shift differences of 0.012 – 0.034 mm/s occurring in both high temperature and low temperature structures can be attributed to different distributions of the RbI ions within the unit cell of RbMn[Fe(CN)6]·H2O.
Highlights
IntroductionTheoretical analysis of 57Fe Mossbauer isomer shifts in a Prussian blue analogueRbMn[Fe(CN)6]·H2O is carried out
In the present work, theoretical analysis of 57Fe Mossbauer isomer shifts in a Prussian blue analogueRbMn[Fe(CN)6]·H2O is carried out
RbMn[Fe(CN)6]·H2O, iron can be present either in the FeII or FeIII oxidation states depending on the charge transfer between iron and manganese
Summary
Theoretical analysis of 57Fe Mossbauer isomer shifts in a Prussian blue analogueRbMn[Fe(CN)6]·H2O is carried out. Theoretical analysis of 57Fe Mossbauer isomer shifts in a Prussian blue analogue. Prussian blue analogues are compounds with the general molecular formula AxMa[Mb(CN)6]·zH2O (where, A = alkali cation and Ma/Mb = metal ion), which attract considerable interest due to their peculiar magneto-optical properties [1]. RbMn[Fe(CN)6]·H2O shows light and temperature induced switching of magnetization [2]. Upon cooling from 300K to approximately 150K, RbMn[Fe(CN)6]·H2O undergoes transition to a state with higher molar magnetization. A reversed transition to a low magnetization state is observed upon heating to ca. It has been hypothesized that the switching of magnetization occurs due to electron transfer from the MnII cations to the FeIII ions (and reversed transition) as a result of structural phase transition upon cooling/heating the samples [3]
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