  In the Fe-Mo based B-site ordered double-perovskite, A2FeMoO6.0, with iron in
the mixed-valence II/III state, the valence value of Fe is not precisely fixed
at 2.5 but may be fine-tuned by means of applying chemical pressure at the
A-cation site. This is shown through a systematic 57Fe Mossbauer spectroscopy
study using a series of A2FeMoO6.0 [A = (Ba,Sr) or (Sr,Ca)] samples with high
degree of Fe/Mo order, the same stoichiometric oxygen content and also almost
the same grain size. The isomer shift values and other hyperfine parameters
obtained from the Mossbauer spectra confirm that Fe remains in the
mixed-valence state within the whole range of A constituents. However, upon
increasing the average cation size at the A site the precise valence of Fe is
found to decrease such that within the A = (Ba,Sr) regime the valence of Fe is
closer to II, while within the A = (Sr,Ca) regime it is closer to the actual
mixed-valence II/III state. As the valence of Fe approaches II, the difference
in charges between Fe and Mo increases, and parallel with this the degree of
Fe/Mo order increases. Additionally, for the less-ordered samples an increased
tendency of clustering of the anti-site Fe atoms is deduced from the Mossbauer
data.
