Beyond density functional theory: the multiconfigurational approach to model heterogeneous catalysis

Catalytic processes are crucially important for many practical chemical applications. Heterogeneous catalysts are especially appealing because of their high stability and the relative ease with which they may be recovered and reused. Computational modeling can play an important role in the design of more catalytically active materials through the identification of reaction mechanisms and the opportunity to assess hypothetical catalysts in silico prior to experimental verification. Kohn–Sham density functional theory (KS-DFT) is the most commonly used method in computational catalysis because it is affordable and it gives results of reasonable accuracy in many instances. Furthermore, it can be employed in a “black-box” mode that does not require significant a priori knowledge of the system. However, KS-DFT has some limitations: it suffers from self-interaction error (sometime referred to as delocalization error), but a greater concern is that it provides an intrinsically single-reference description of the...