†Department of Physics, ‡Department of Materials Science and Engineering, §Department of Chemistry, and ∥Materials Research Institute, Pennsylvania State University, University Park, Pennsylvania 16802, United States.
Nano Lett. 2015 Aug 12;15(8):5124-30. doi: 10.1021/acs.nanolett.5b01343. Epub 2015 Aug 3.
Slow decompression of crystalline benzene in large-volume high-pressure cells has recently achieved synthesis of a novel one-dimensional allotrope of sp(3) carbon in which stacked columns of benzene molecules rehybridize into an ordered crystal of nanothreads. The progenitor benzene molecules function as six-valent one-dimensional superatoms with multiple binding sites. Here we enumerate their hexavalent bonding geometries, recognizing that the repeat unit of interatomic connectivity ("topological unit cell") need not coincide with the crystallographic unit cell, and identify the most energetically favorable cases. A topological unit cell of one or two benzene rings with at least two bonds interconnecting each adjacent pair of rings, accommodates 50 topologically distinct nanothreads, 15 of which are within 80 meV/carbon atom of the most stable member. Optimization of aperiodic helicity reveals the most stable structures to be chiral. We generalize Euler's rules for ring counting to cover this new form of very thin one-dimensional carbon, calculated their physical properties, and propose a naming convention that can be generalized to handle nanothreads formed from other progenitor molecules.
最近,通过在大容量高压釜中缓慢减压,成功合成了一种新型的 sp(3) 碳一维同素异形体,其中堆积的苯分子柱重新杂化成有序的纳米线晶体。前体苯分子作为具有多个结合位点的六价一维超原子发挥作用。在这里,我们列举了它们的六价键合几何形状,认识到原子间连接的重复单元(“拓扑单元胞”)不一定与晶胞重合,并确定了最有利的情况。一个或两个苯环的拓扑单元胞,至少有两个键将每个相邻的环连接起来,可以容纳 50 个拓扑上不同的纳米线,其中 15 个与最稳定成员的距离在 80 meV/碳原子以内。非周期性螺旋的优化揭示了最稳定的结构是手性的。我们将环计数的欧拉规则推广到覆盖这种非常薄的一维碳的新形式,计算了它们的物理性质,并提出了一种命名惯例,可以推广到处理由其他前体分子形成的纳米线。
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