First-principles modelling of the new generation of subnanometric metal clusters: Recent case studies

Abstract

The very recent development of highly selective techniques making possible the synthesis and experimental characterization of subnanometric (subnanometer-sized) metal clusters (even single atoms) is pushing our understanding far beyond the present knowledge in materials science, driving these clusters as a new generation of quantum materials at the lower bounds of nanotechnology. When the size of the metal cluster is reduced to a small number of atoms, the d-band of the metal splits into a subnanometric d-type molecular orbitals network in which all metal atoms are inter-connected, with the inter-connections having the length of a chemical bond (1-2 Å). These molecular characteristics are at the very core of the high stability and novel properties of the smallest metal clusters, with their integration into colloidal materials interacting with the environment having the potential to further boost their performance in applications such as luminescence, sensing, bioimaging, theranostics, energy conversion, catalysis, and photocatalysis. Through the presentation of very recent case studies, this Feature Article is aimed to illustrate how first-principles modelling, including methods beyond the state-of-the-art and an interplay with cutting-edge experiments, is helping to understand the special properties of these clusters at the most fundamental level. Moreover, it will be discussed how superfluid helium droplets can act both as nano-reactors and carriers to achieve the synthesis and surface deposition of metal clusters. This concept will be illustrated with the quantum simulation of the helium droplet-assisted soft-landing of a single Au atom onto a titanium dioxide (TiO₂) surface. Next, it will be shown how the application of first-principles methods have disclosed the fundamental reasons why subnanometric Cu₅ clusters are resistant to irreversible oxidation, and capable of increasing and extending into the visible region the solar absorption of TiO₂, of augmenting its efficiency for photo-catalysis beyond a factor of four, also considering the decomposition and photo-activation of CO₂ as a prototypical (photo-) catalytic reaction. Finally, I will discuss how the modification of the same material with subnanometric Ag₅ clusters has converted it into a "reporter" of a surface polaron property as well as a novel two-dimensional polaronic material.

Keywords: Ab initio post-Hartree-Fock methods; Air-stability; Catalysts; Copper clusters; Density functional theory; First-principles modelling; Helium droplets; Metal clusters; Optical properties; Oxidation; Photo-induced processes; Photocatalysts; Polaronic materials; Quantum effects; Silver clusters; Single atomic gold; Single metal atoms; Soft-landing; Structural fluxionality; Subnanometric materials; Surface deposition; Titanium dioxide; UV-Vis absorption spectra; Wet-chemical synthesis.