The Influence of Carbon Doping on the Structures, Properties, and Stability of Beryllium Clusters

Abstract

The global minimum structures of the carbon‐doped Ben (n = 1–12) clusters are obtained at the B3PW91/6‐311+G(d) level and compared with those of pure beryllium clusters. It is found that the carbon dopant prefers to be located outside the host Ben cage and tends to be tetracoordinated. The evolution of the electronic and energetic properties of BenC is studied using the QCISD(T) method. Results show that the introduction of carbon doping strengthens intracluster interaction of beryllium clusters. Besides, the Be3C and Be8C clusters, with their particular stability, are considered as magic‐number clusters in the BenC series. Molecular‐orbital (MO) analysis indicates that both clusters have fully filled electron shells, whereas the contribution of the carbon atomic orbital leads to MO energy‐level disorder of the BenC clusters.

Degradation of Tetracycline on SiO2-TiO2-C Aerogel Photocatalysts under Visible Light

“…The band gap energy of the carbon-doped photocatalysts is significantly reduced, causing red shifting of the absorption edge to 400–500 nm, and extending the absorption wavelength response range to the visible light region. Carbon doping may lead to an energy-level disorder of the hybrid orbital between the C 2p and the O 2p [ 51 ], which may be caused by the partial substitution of C atom for O atom. This promotes the micro-transformation of the TiO 2 lattice to form a new energy level with a smaller band gap.…”

On reactivity of superatom Be8C with nucleophiles to produce hydrogen

“…The lowest‐energy structure of Be 8 C is a mono‐capped square antiprism with C 4 v symmetry (see Figure 1). Besides high binding energy and dissociation energy, Be 8 C also features a large HOMO‐LUMO gap of 3.382 eV [30], which is much larger than that of stable superatom anion Al 13 − (2.690 eV, computed at the same level). These indicate considerable stability of the Be 8 C cluster.…”

“…Based on previous study of the Be n C clusters [30], the economical B3PW91 functional [30][31][32][33] was adopted, along with the 6-311++G(d, p) basis set, to obtain the optimized structures in this work. Harmonic vibrational frequency analysis was performed at the same level to ensure that the optimized structures correspond to transition states or true minima on the potential energy surfaces.…”

“…Our previous study has reported a magic cluster, namely Be 8 C, which stands out among the Be n C series [30] with unique relative stability [20] and hence, may serve as a "superatomic" building block for nanoscale assemblies or materials. According to valence molecular orbital (MO) analysis, we notice that Be 8 C possesses a closed-shell electron configuration of 1S 2 1P 6 1D 4 2S 2 1D 6 , which is similar to that of 3s 2 3p 6 3d 10 4s 2 for Zn atom except that the 1D level of Be 8 C splits due to its non-spherical geometry (see Figure S1).…”

Hydrogen evolution reaction of Ben + H2O (n = 5–9) based on density functional theory

“…The molecular geometry and characteristics of pure beryllium clusters and doped beryllium clusters have drawn a lot of interest because beryllium clusters have a distinctive electronic structure. 12–17 Srinivas et al . 12 investigated the geometric structure and electronic properties of small beryllium clusters in the gradient-corrected density functional theory.…”