Theoretical Insights into the Geometrical Evolution, Photoelectron Spectra, and Vibrational Properties of YGe(n)(–) (n = 6–20) Anions: From Y-Linked to Y-Encapsulated Structures

[Image: see text] The structural evolution behavior of germanium anionic clusters doped with the rare-earth metal yttrium, YGe(n)(–) (n = 6–20), has been investigated using a mPW2PLYP density functional scheme and an ABCluster structure searching technique. The results reveal that with increasing cluster size n, the structure evolution pattern is from the Y-linked framework (n = 10–14), where Y serves as a linker (the Y atom bridges two germanium subclusters), to the Y-encapsulated framework (n = 15–20), where the Y atom is located in the center of the Ge cage. The simulated PES spectra show satisfying agreement with the experimental PES spectra for n = 12–20, which reveals that the global minimum structures reported here are reliable. In particular, the anionic YGe(16)(–) nanocluster is found to be the most stable structure in the size range of n = 6–20 through analyzes of the relative stability, highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap, spherical jellium model, and isochemical shielding surface. Moreover, spectral properties such as infrared and Raman spectra were reported. In addition, the UV–vis spectra of the YGe(16)(–) nanocluster are in good agreement with solar energy distribution, showing that such substances serve as multifunctional building blocks to be potentially used in optoelectronic devices or solar energy converters.