Automated, Consistent, and Even-Handed Selection of Active Orbital Spaces for Quantum Embedding.

A widely used strategy to reduce the computational cost of quantum-chemical calculations is to partition the system into an active subsystem, which is the focus of the computational efforts, and an environment that is treated at a lower computational level. The system partitioning is mostly based on localized molecular orbitals. When reaction paths or energy differences are to be calculated, it is crucial to keep the orbital space consistent for all structures. Inconsistencies in orbital space can lead to unpredictable errors on the potential energy surface. While successful strategies to ensure this consistency have been established for organic and even metal-organic systems, these methods often fail for metal clusters or nanoparticles with a high density of near-degenerate and delocalized molecular orbitals. However, such systems are highly relevant for catalysis. Accurate yet feasible quantum-mechanical ab initio calculations are therefore highly desired. In this work, we present an approach based on the subsystem projected atomic orbital decomposition algorithm that allows us to ensure automated and consistent partitioning even for systems with delocalized and near-degenerate molecular orbitals and demonstrate the validity of this method for the binding energies of small molecules on transition-metal clusters.