Probing the structures, stabilities, and electronic properties of neutral and charged carbon-doped lithium CLi( n = 2-20, μ = 0, ±1) clusters from unbiased CALYPSO method.

The structural and electronic properties of the global minimum structures of neutral, anionic and cationic CLi( n = 2-20; μ = 0, ±1) clusters were systematically investigated using the unbiased CALYPSO structure searching method in conjunction with density functional theory calculations at the B3LYP/6-311+G* level of theory. It was found that the ground-state structures of neural CLi clusters exhibit linear and planar configurations at n = 2 and 3, respectively, above which three-dimensional configurations are preferred with C and several Li atoms encapsulated into the Li cages. There were only minor differences in the structure between the neutral and charged CLi clusters, which is in accordance with the calculated results of ionization potential and electron affinity. However, the addition/removal of one electron to/from the neutral species had a significant effect on the stabilities of the resulting charged clusters. The averaged binding energy indicated that cationic CLi clusters show relatively higher stabilities. Pronounced odd-even alternations were observed in the fragmentation energy, second-order energy difference and HOMO-LUMO energy gaps. Finally, detailed chemical bonding of the CLi cluster was analyzed based on the AdNDP method, and static polarizabilities of CLi clusters are discussed. [ABSTRACT FROM AUTHOR]