Cooperativity of Spin Crossover Complexes: Combining Periodic Density Functional Calculations and Monte Carlo Simulations

The total enthalpies of the 16 different spin configurations that can be realized in the unit cell of the archetype spin crossover complex [Fe(phen) [Formula: see text] (NCS) [Formula: see text]] (phen = 1,2-phenanthroline) were calculated, applying periodic density functional theory combined with the Hubbard model and the Grimme-D2 dispersion correction (DFT+U+D2). The obtained enthalpy differences between the individual spin configurations were used to determine spin couplings of an Ising-like model, and subsequent Monte Carlo simulations for this model allowed the estimation of the phenomenological interaction parameter Γ of the Slichter–Drickamer model, which is commonly used to describe the cooperativity of the spin transition. The calculation procedure described here—which led to an estimate of about 3 kJ·mol [Formula: see text] for Γ, in good agreement with experiment—may be used to predict from first principles how modifications of spin crossover complexes can change the character of the spin transition from gradual to abrupt and vice versa.