Actinide-embedded gold superatom models: Electronic structure, spectroscopic properties, and applications in surface-enhanced Raman scattering
actinide element, DFT calculation, gold nanoparticle, superatomic orbital, surface-enhanced Raman scattering
Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared with that of the isoelectronic entities [Ac@Au14]− and [Pa@Au14]+ using density functional theory. The calculation results indicate that these clusters all adopt a closedshell superatomic 18-electron configuration of the 1S21P61D10 Jellium state. The absorption spectrum of Th@Au14 can be interpreted by the Jelliumatic orbital model. In addition, calculated spectra of pyridine-Th@Au14 complexes in the blue laser band exhibit strong peaks attributable to charge transfer (CT) from the metal to the pyridine molecule. These charge-transfer bands lead to a resonant surface-enhanced Raman scattering (SERS) enhancement of ~104. This work suggests a basis for designing and synthesizing SERS substrate materials based on actinide-embedded gold superatom models.
Tsinghua University Press
Yang Gao,Bo Wang,Yanyu Lei,Boon K. Teo,Zhigang Wang, Actinide-embedded gold superatom models: Electronic structure, spectroscopic properties, and applications in surface-enhanced Raman scattering. NanoRes.2016, 9(3): 622–632