Structural evolution, stability, electronic and bonding properties of sodium-doped magnesium cluster cations

AbstractBimetallic sodium-doped magnesium cluster cations, NaMgn+(n= 2–12), have been investigated through a synergetic combination of the CALYPSO code and DFT calculations. The results reveal that the lowest-energy structures of NaMgn+ exhibit linear, planar, triangular pyramid, pentagonal pyramid, and triangular prism topologies. The structures can be described as a substituted geometry of pure Mg clusters at the small size. Starting from n = 9, the dominant structures transform into a triangular prism-based configuration. Like anionic and neutral NaMgn clusters, the Na atom prefers the peripheral regions of the Mgn framework. Stability studies indicate NaMg4+ and NaMg10+ to be the~most stable clusters, which may benefit from their closed-shell electron structures. Analysis of the bonding nature shows stronger Mg-Mg interaction than the Na-Mg interaction in the NaMg4+ and NaMg10+ clusters. The reason is that covalent bonds are formed in the Mg-Mg regions, while there is no aggregation of electron density in the Na-Mg regions.KEYWORDS: DFTCALYPSONaMgn+ clustersstructureselectronic properties Disclosure statementNo potential conflict of interest was reported by the author(s).Additional informationFundingThis work was supported by the Natural Science Basic Research Plan in Shaanxi Province of China (grant number 2023-JC-YB-464).