Adsorption Sites on Pd Nanoparticles Unraveled by Machine-Learning Potential with Adaptive Sampling

Catalytic properties of noble-metal nanoparticles (NPs) are largely determined by their surface morphology. The latter is probed by surface-sensitive spectroscopic techniques in different spectra regions. A fast and precise computational approach enabling the prediction of surface–adsorbate interaction would help the reliable description and interpretation of experimental data. In this work, we applied Machine Learning (ML) algorithms for the task of adsorption-energy approximation for CO on Pd nanoclusters. Due to a high dependency of binding energy from the nature of the adsorbing site and its local coordination, we tested several structural descriptors for the ML algorithm, including mean Pd–C distances, coordination numbers (CN) and generalized coordination numbers (GCN), radial distribution functions (RDF), and angular distribution functions (ADF). To avoid overtraining and to probe the most relevant positions above the metal surface, we utilized the adaptive sampling methodology for guiding the ab initio Density Functional Theory (DFT) calculations. The support vector machines (SVM) and Extra Trees algorithms provided the best approximation quality and mean absolute error in energy prediction up to 0.12 eV. Based on the developed potential, we constructed an energy-surface 3D map for the whole Pd(55) nanocluster and extended it to new geometries, Pd(79), and Pd(85), not implemented in the training sample. The methodology can be easily extended to adsorption energies onto mono- and bimetallic NPs at an affordable computational cost and accuracy.