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

Area of Science:

• Computational chemistry
• Materials science
• Catalysis

Background:

• The catalytic activity of metal nanoclusters is highly dependent on their atomic structure.
• Standard computational methods like density functional theory (DFT) struggle to accurately model the complex metal-metal and metal-support interactions in these systems.
• Coupled cluster theory, specifically CCSD(T), offers high accuracy but is computationally prohibitive for large nanoclusters.

Purpose of the Study:

• To develop and validate accurate and computationally feasible methods for simulating oxide-supported metal nanoclusters.
• To benchmark the performance of existing protocols and introduce a new correction method for DFT.
• To enable reliable predictions of nanocluster structures, aiding in the design of advanced catalysts.

Main Methods:

• Application of the SKZCAM protocol for benchmarking oxide-supported nanoclusters.
• Development of a coupled cluster (CC) correction (ΔCC) to address DFT's limitations in modeling metal-metal interactions.
• Utilizing CCSD(T) calculations to achieve high accuracy at a reduced computational cost.

Main Results:

• The SKZCAM protocol provides the first benchmarks, highlighting DFT's deficiencies in capturing metal-metal interactions.
• The proposed ΔCC correction achieves accuracy comparable to SKZCAM but with significantly lower computational expense.
• A ground-state structure for Au20 on MgO was identified, resolving conflicting predictions from previous DFT models and agreeing with experimental data.

Conclusions:

• The developed ΔCC approach makes accurate CCSD(T) calculations accessible for oxide-supported nanoclusters.
• This method facilitates the study of larger, more complex nanocluster systems with reliable accuracy.
• The findings pave the way for improved computational design of highly active and selective catalysts.