Going for Gold(-Standard): Attaining Coupled Cluster Accuracy in Oxide-Supported Nanoclusters

The structure of oxide-supported metal nanoclusters plays an essential role in their sharply enhanced catalytic activity over that of bulk metals. Simulations provide the atomic-scale resolution needed to understand these systems. However, the sensitive mix of metal–metal and metal–support interactions, which govern their structure, puts stringent requirements on the method used, requiring calculations beyond standard density functional theory (DFT). The method of choice is coupled cluster theory [specifically CCSD(T)], but its computational cost has so far prevented its application to these systems. In this work, we showcase two approaches to make CCSD(T) accuracy readily achievable in oxide-supported nanoclusters. First, we leverage the SKZCAM protocol to provide the first benchmarks of oxide-supported nanoclusters, revealing that it is specifically metal–metal interactions that are challenging to capture with DFT. Second, we propose a CCSD(T) correction (ΔCC) to the metal–metal interaction errors in DFT, reaching accuracy comparable to that of the SKZCAM protocol at significantly lower cost. This approach forges a path toward studying larger systems at reliable accuracy, which we highlight by identifying a ground-state structure in agreement with experiments for Au20 on MgO, a challenging system where DFT models have yielded conflicting predictions.