Going for Gold(-Standard): Attaining Coupled Cluster Accuracy in Oxide-Supported Nanoclusters (2311.01426v2)

Abstract: The structure of oxide-supported metal nanoclusters plays an essential role in their sharply enhanced catalytic activity over 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 going 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 applications. 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 ($\Delta$CC) to the metal-metal interaction errors in DFT, reaching comparable accuracy to the SKZCAM protocol at significantly lower cost. This forges a path towards studying larger systems at reliable accuracy, which we highlight by identifying a ground state structure in agreement with experiments for Au$_{20}$ on MgO; a challenging system where DFT models have yielded conflicting predictions.