On the accuracy of density functional theory in transition metal chemistry

Abstract

Density Functional Theory has become very widely used to study the electronic structure and related properties of transition metal complexes. Despite the many successes obtained using modern functionals, care is still needed as quite large errors can occur. These can be best understood by taking into consideration how density functional theory works, and how well it performs for the simpler case of main-group compounds. This serves to highlight the critical role of the exchange functional, which describes such varied effects as electron self-interaction, static (or non-dynamic) correlation, and dynamic correlation. A poor balance between these effects can lead to significant errors even for main-group compounds. This is even truer for transition metal compounds. Benchmark data published in the last year suggest that all existing functionals can lead to severe errors for some transition metal compounds. There is a slight trend for systems involving more static correlation to be treated better using second- or third-generation gradient-corrected or kinetic energy density functionals, rather than hybrid functionals. This trend is however quite variable from one type of compound to another. Computed spin-state splittings are highly variable from one functional to another, and this is also diagnostic of differences in the extent of static correlation. The increasing awareness of transition metal compounds by the developers of new exchange–correlation functionals should lead in the medium term to more accurate and hence (even) more useful functionals.