Based on the super valence bond (SVB) model, a motif of face‐sharing bi‐tetrahexahedral superatomic molecules M₁M₂@Li₂₀ (M₁/M₂ = Ti and W) was recently constructed by fusion of two tetrahexahedral superatoms Ti@Li₁₄ and W@Li₁₄. Here, as an extension of the formation of molecules from superatoms, binary lithium clusters W₂Li_n (n = 14‐19) are studied in conjunction with particle swarm optimization algorithm search and density functional theory calculations. The lowest‐lying isomers of W₂Li_n (n = 15‐19) with the magnetic moments of 0 to 3 μ_B are identified as superatomic molecules by analysis of their molecular orbitals and chemical bonding patterns, whereas the global minimum isomer of W₂Li₁₄ does not possess the geometric structure of monomer. Via a lithium atom sequentially removed, a series of superatomic bond orders of 3, 3.5, 4, and 4.5 are exposed, reminiscent of classical chemical bonds. Meanwhile, many isosupermolecules are found in the low‐energy structures, predicting the diversity assembly of superatom materials. Our results highlight the tremendous opportunities for molecules assembled by superatoms, which may be in favor of the designs of nanoparticles or functional materials in future according to the SVB model.

中文翻译：

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磁性二元锂团簇W2Lin（n = 15-19）：“双超原子分子”的理论预测

基于超价键（SVB）模型，最近通过融合两个四面体超原子Ti构造了面部共享的双四面体超原子分子M ₁ M ₂ @Li ₂₀（M ₁ / M ₂ = Ti和W）的基序@Li ₁₄和W @ Li ₁₄。在这里，作为由超原子形成分子的扩展，结合粒子群优化算法搜索和密度泛函理论计算，研究了二元锂团簇W ₂ Li _n（n = 14-19）。W ₂ Li _n（n= 15-19），用0至3的磁矩μ_乙被识别为通过分子轨道和化学键模式的分析superatomic分子，而W的全局最小异构体₂李₁₄不具有单体的几何结构。通过依次去除的锂原子，暴露出一系列的3、3.5、4和4.5的超原子键序，让人联想到经典的化学键。同时，在低能结构中发现许多异超分子，预示了超原子材料的多样性组装。我们的结果凸显了由超原子组装的分子的巨大机会，根据SVB模型，这可能有利于未来纳米颗粒或功能材料的设计。