ABSTRACT This study systematically explores the structural, electronic, and bonding characteristics of C 2 B n ( n = 2–12) clusters through a combination of CALYPSO global structure searches and density functional theory (DFT) computations. The influence of carbon incorporation on the geometric evolution, energetic stability, and bonding nature of boron clusters is comprehensively analyzed. The C 2 B 6 cluster demonstrates superior stability, which can be primarily attributed to its well‐balanced charge distribution and the synergistic σ –π conjugation occurring between the localized boron–boron bonds and the delocalized boron–carbon bonds. Detailed electronic structure analyses employing Natural Bond Orbital (NBO), Electron Localization Function (ELF), Adaptive Natural Density Partitioning (AdNDP), and Interaction Region Indicator (IRI) methods demonstrate that charge transfer mainly occurs from boron to carbon through B‐ 2p and C‐ 2p orbital coupling, resulting in delocalized multicenter bonding networks. These findings enhance the fundamental understanding of boron–carbon bonding mechanisms and offer significant theoretical insights for the rational design of novel boron–carbon nanomaterials.
Wáng et al. (Mon,) studied this question.