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

Abstract

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.