Benchmarks for transition metal spin-state energetics: why and how to employ experimental reference data?

Abstract

Accurate prediction of energy differences between alternative spin states of transition metal complexes is essential in computational (bio)inorganic chemistry—for example, in characterization of spin crossover materials and in the theoretical modeling of open-shell reaction mechanisms—but it remains one of the most compelling problems for quantum chemistry methods. A part of this challenge is to obtain reliable reference data for benchmark studies, as even the highest-level applicable methods are known to give divergent results. This Perspective discusses two possible approaches to method benchmarking for spin-state energetics: using either theoretically computed or experiment-derived reference data. With the focus on the latter approach, an extensive general review is provided for the available experimental data of spin-state energetics and their interpretations in the context of benchmark studies, targeting the possibility of back-correcting the vibrational effects and the influence of solvents or crystalline environments. With a growing amount of experience, these effects can be now not only qualitatively understood, but also quantitatively modeled, providing the way to derive nearly chemically accurate estimates of the electronic spin-state gaps to be used as benchmarks and advancing our understanding of the phenomena related to spin states in condensed phases.