The structure and properties of (CuCl)n (n = 2–15)

The stable structures of (CuCl) n ( n = 2–15) were optimized by combining a genetic algorithm with the DFT/PBE method. In addition to previously reported low-energy structures, several new lower-energy isomers were located. For (CuCl) n clusters, planar configurations are predominant at n = 2–3, whereas non-planar motifs prevail starting from n = 4. Stacked structures are favored for n = 6–11, while cage-like geometries become dominant at n = 12. Clusters with n = 3, 6, 9, and 12 are identified as magic-number clusters. The clusters possess high vertical ionization potentials (7.68–9.65 eV) and low vertical electron affinities (0.28–3.84 eV). Meanwhile, multiple types of bonding coexist within these clusters: electrostatic interactions dominate, together with Cu-Cl/Cu-Cu covalent bonds and stacking-based noncovalent forces. We also calculated their spectra, polarizability and hyperpolarizability, and investigated magnetically induced currents and chemical reactivity of typical isomers. • Some low-energy isomers of novel (CuCl) n ( n = 2–15) clusters have been discovered. • Structural evolution rules of (CuCl)ₙ clusters across n = 2–15 is revealed. • Ionic, covalent and noncovalent interactions in CuCl clusters are fully analyzed. • Spectroscopic, electric/magnetic field responses and chemical reactivity of these clusters are characterized.