Quantum Chemistry Study on the Structures and Electronic Properties of Bimetallic Ca2-Doped Magnesium Ca2Mgn (n = 1–15) Clusters

Abstract

Here, by utilizing crystal structure analysis through the particle swarm optimization (CALYPSO) structural searching method with density functional theory (DFT), we investigate the systemic structures and electronic properties of Ca2Mgn (n = 1–15) clusters. Structural searches found that two Ca atoms prefer to occupy the external position of magnesium-doped systems at n = 2–14. Afterward, one Ca atom begins to move from the surface into the internal of the caged skeleton at n = 15. Calculations of the average binding energy, second-order difference of energies, and HOMO–LUMO gaps indicated that the pagoda construction Ca2Mg8 (as the magic cluster) has higher stability. In addition, the simulated IR and Raman spectra can provide theoretical guidance for future experimental and theoretical investigation. Last, further electronic properties were determined, including the charge transfer, density of states (DOS) and bonding characteristics. We hope that our work will provide theoretical and experimental guidance for developing magnesium-based nanomaterials in the future.

Probing the effects of lithium doping on structures, properties, and stabilities of magnesium cluster anions

“…In cluster structure prediction, many studies have successfully revealed its validity. [42][43][44][45][46][47][48][49][50] For each cluster size, there are more than 800 structurally different isomers located at 20 generations. It provides 50 structures in each generation, 70% of which are generated by PSO and the rest are newly produced.…”

Theoretical investigations on the structures and electronic and optical properties of neutral and anionic M2-doped B24clusters (M = Li, Na, and K)

“…Moreover, numerous structures based on the CALYPSO searching method have been executed successfully for clusters, two-dimensional materials, functional materials and crystals. 39–51 The detailed searching process could be summarized as follows: first, the PBE/3-21G level was used for the preliminary structures. Second, according to the parameters of generation (50) and maxstep (20), about 1000 initial structures can be obtained.…”