Structural Evolution, Electronic Structures, and Vibrational Properties of Anionic LuGen (n = 5-17) Clusters: From Lu-Linked to Lu-Encapsulated Configurations.

Abstract

The structural evolution pattern and electronic properties of Lu-doped germanium anion clusters, LuGen- (n = 5-17), have been investigated using a global search method combined with a double hybrid density functional theory and by comparing the theoretical PES spectra with the experimental ones. It is found that, for the structural growth patterns, a Lu-linked configuration is preferred for n = 10-14 in which the Lu atom as a linker connects two Ge subclusters and a Lu-encapsulated Ge cage-like motif is preferred for n = 15-17. The simulated PES spectra agree with experimental ones, revealing that the current global minimum structures are the true minima. The properties such as relative stability, charge transfer, highest-energy occupied molecular orbital-lowest-energy unoccupied molecular orbital (HOMO-LUMO) gap, IR, Raman, and ultraviolet-visible (UV-vis) spectra have been evaluated. The results of IR and Raman spectra could provide additional ways to experimentally identify the structure of these clusters. The results of stability, HOMO-LUMO gap, and UV-vis spectra could make the LuGe16- cluster the most suitable building block for further development as a potential optoelectronic material.