Microscopic modeling of a spin crossover transition

In spin crossover materials, an abrupt phase transition between a low-spin state and a high-spin (HS) state can be driven by temperature, pressure or by light irradiation. Of special relevance are Fe(II) based coordination polymers where, in contrast to molecular systems, the phase transition between a spin S = 0 and 2 state shows a pronounced hysteresis which is desirable for technical applications. A satisfactory microscopic explanation of this large cooperative phenomenon has been sought for a long time. The lack of x-ray data has been one of the reasons for the absence of microscopic studies. In this work, we present an efficient route to prepare reliable model structures and within an ab initio density functional theory analysis and effective model considerations we show that in polymeric spin crossover compounds magnetic exchange between HS Fe(II) centers is as important as elastic couplings for understanding the phase transition. We discuss the relevance of these interactions for the cooperative behavior in these materials.