Possible reaction coordinates in the metastable states of sodiumnitroprusside Na₂[Fe(CN)₅NO]2H₂O: a discussion based on neutron diffraction- and spectroscopic measurements

Abstract:

The metastable states of sodiumnitroprusside Na₂[Fe(CN)₅NO]2H/D₂O are extremely stable at temperatures below 200 K. It is possible to allocate structural changes measured by neutron diffraction to measured spectroscopic parameters, but the amount of the structural change is relatively small for a reaction co-ordinate as the metastable states have an extremely long lifetime. New hypotheses for related systems try to explain such a phenomena in two ways: The first way is a 90^o bending of the NO-bond in the metastable state, the second one an exchange of the oxygen and nitrogen atoms in the NO-bond (which can be regarded as an 180^o bending). As such changes would be possible also from our density functional calculations, we re-investigated our neutron diffraction data using the new models. However, our results are not compatible with one of these models. On the contrary, the neutron diffraction data show partially opposite tendencies. We compare both models with EXAFS measurements, with vibrational spectroscopic results and the data found by Mössbauer spectroscopy. We propose a potential scheme for all three states (GS, MS_I and MS_II) extracted from absorption and thermodynamic data to explain the electronic and energetic rearrangement, and the population dynamics.