Prediction of beryllium clusters (Be; n = 3-25) from first principles

Evolutionary searches using the USPEX method (Universal Structure Predictor: Evolutionary Xtallography) combined with density functional theory (DFT) calculations were performed to obtain the global minimum structures of beryllium (Be, n = 3-25) clusters. The thermodynamic stability, optoelectronic and photocatalytic properties as well as the nature of bonding are considered for the most stable clusters. It is found that the cluster with n = 15 is the transition point at which the configurations change from 3D hollow cages to filled cage structures (with an interior atom appearing in the structure). All the ground state structures are energetically favorable with negative binding energies, suggesting good synthetic feasibility for these structures. The calculated relative stabilities and electronic structure show that the Be₄, Be₁₀ and, Be₁₇ clusters are the most stable structures and can be considered as superatoms. The electron configurations of Be₄, Be₁₀ and Be₁₇ clusters with 8, 20 and 34 electrons are identified as 1S² 1P⁶, 1S² 1P⁶ 1D¹⁰ 2S², 1S² 1P⁶ 1D¹⁰ 2S² 1F¹⁴, respectively. Theoretical simulations determined that all the ground state structures exhibit excellent thermal stability, where the upper-limit temperature that the structures can tolerate is 900 K. During AIMD simulation of O₂ adsorption onto the Be₁₇ cluster an interesting phenomenon was happening in which the pristine Be₁₇ cluster becomes a new stable Be₁₇O₁₆ cluster. Based on ELF (electron localization function) analysis, it can be concluded that the Be-Be bonds in the small clusters are primarily of van der Waals type, while for the larger clusters, the bonds are of metallic nature. The Be clusters show very strong absorption in the UV and visible regions with absorption coefficients larger than 10⁵ cm^-1, which suggests a wide range of potential advanced optoelectronics applications. The Be₁₇ cluster has a suitable band alignment in the visible-light excitation region which will produce enhanced photocatalytic activities (making it a promising material for water splitting).