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Ab initio calculations; Transition metals; Coupled-cluster theory; Multireference correlation methods
Abstract:
In this commentary the challenges faced in the application of wavefunction-based ab initio methods to (open-shell) transition metal complexes of (bio)inorganic interest are briefly touched on. Both single-reference and multireference methods are covered. It is stressed that the generation and nature of the reference wavefunction is a subject of major importance. How erroneous results can be easily obtained even with coupled-cluster theory is illustrated through the example of the septet–quintet separation in iron(IV)–oxo complexes. Second, the interplay between relativistic and correlation effects is important. This is demonstrated with coupled-cluster calculations on models for dinuclear copper active sites, where relativity has a major influence on the relative stabilities of the bis(μ-oxo) and side-on peroxo species.
