Theoretical Study on Structural Behaviors and Optical Properties of Silver‐Doped Silicon Anion Clusters <scp>AgSi</scp> <i> _n </i> ⁻ <i>n</i> = 3–20

ABSTRACT Silver metal‐doped silicon clusters possess properties that are crucial for advancing microelectronics, catalysis, and energy storage technologies. In the present study, the equilibrium geometry and the growth pattern of silver‐doped silicon anionic cluster AgSi n − n = 3 – 20 were systematically studied using mPW2PLYP schemes in combination with the global search technique. The growth pattern of AgSi n − clusters can be summarized as follows: For n = 3–10, the Ag atom is adsorbed on the surface of the pure Si n structure; starting at n = 11, the configuration transitions to a substitutional type where an Ag atom replaces a Si atom in the pure Si n +1 structure. Simulated photoelectron spectroscopy (PES) and Raman spectra, which are employed for structural identification, are presented and compared with previously reported experimental PES. Besides that, the relative stabilities, HOMO–LUMO gaps, and natural population analysis were also performed. This study provides theoretical insights for the future discovery of novel functional cluster nanomaterials.