Periodic density functional theory study of spin crossover in the cesium iron hexacyanochromate prussian blue analog.

This paper presents a detailed theoretical analysis of the electronic structure of the CsFe[Cr(CN)(6)] prussian blue analog with emphasis on the structural origin of the experimentally observed spin crossover transition in this material. Periodic density functional calculations using generalized gradient approximation (GGA)+U and nonlocal hybrid exchange-correlation potentials show that, for the experimental low temperature crystal structure, the t(2g)(6) e(g)(0) low spin configuration of Fe(II) is the most stable and Cr(III) (S = 3/2, t(2g)(3) e(g)(0)) remains the same in all cases. This is also found to be the case for the low spin GGA+U fully relaxed structure with the optimized unit cell. A completely different situation emerges when calculations are carried out using the experimental high temperature structure. Here, GGA+U and hybrid density functional theory calculations consistently predict that the t(2g)(4) e(g)(2) Fe(II) high spin configuration is the ground state. However, the two spin configurations appear to be nearly degenerate when calculations are carried out for the geometries arising from a GGA+U full relaxation of the atomic structure carried out at experimental high temperature lattice constant. A detailed analysis of the energy difference between the two spin configurations as a function of the lattice constant strongly suggests that the observed spin crossover transition has a structural origin with non-negligible entropic contributions of the high spin state.