Calculating spin crossover temperatures by a first-principles LDA+ U scheme with parameter U evaluated from GW

Abstract

The prediction of spin crossover (SCO) temperatures (T1/2) depends sensitively on the description of local Coulomb correlation. Due to its balance between accuracy and computational cost, local density approximation combined with Hubbard U model (LDA+U) is an appealing tool for this purpose. Despite its accurate performance on energetic properties, such as spin adiabatic energy difference, it is well-known that the LDA+U approach would lose its predictive power if U is tuned to achieve close agreement with experiment for a certain property. On the other hand, a static U value cannot account for changes in the electronic structure. Here, we propose a framework to derive dynamical U (Udyn) values for iron(ii) complexes from the many-body GW calculations. By performing model calculations on a series of compounds with varying ligand fields, we show that the U values determined in this way are local environment dependent, and the resulting LDA+Udyn method could reproduce their experimental ground spin states. We present applications to selected SCO complexes illustrating that Udyn considerably overcomes some of the drawbacks of employing a constant U in the calculation of thermochemical quantities. Using the described calculation procedure, the T1/2 values are predicted with a small mean absolute error of 176 K with respect to experiment.