Dipole-Modulated Carrier Dynamics and Charge Transport Behavior of Ligand-Protected Metal Chalcogenide Nanoclusters

Atomically precise nanoclusters, distinguished by their unique nuclearity- and structure-dependent properties, hold great promise for applications of energy conversion and electronic transport. However, the relationship between ligands and their properties remains a mystery yet to be unrevealed. Here, the influence of ligands on the electronic structures, optical properties, excited-state dynamics, and transport behavior of Re₁₂S₁₆ dimer clusters with different ligands is explored using density functional theory combined with time-domain nonadiabatic molecular dynamic simulations. The correlation between ligands and the excited-state dynamics of nanoclusters is elucidated. The ligand replacement introduces a built-in electric field at the dimer interface, inhibiting the recombination of excited carriers and increasing the voltage threshold. This study paints a physical picture of the ligand effect on nanoclusters in terms of geometric configuration, electronic structure, optical properties, carrier dynamics, and transport behavior, paving a pathway toward their applications in optoelectronic materials.