Sabirov Denis Sh, Tukhbatullina Alina A
Laboratory of Mathematical Chemistry, Institute of Petrochemistry and Catalysis UFRC RAS, 450075 Ufa, Russia.
Nanomaterials (Basel). 2022 Dec 9;12(24):4404. doi: 10.3390/nano12244404.
Polarizability exaltation is typical for (C) nanostructures. It relates to the ratio between the mean polarizabilities of (C) and C: the first one is higher than the -fold mean polarizability of the original fullerene. This phenomenon is used in the design of novel fullerene compounds and the understanding of its properties but still has no chemical rationalization. In the present work, we studied the distributed polarizability of (C) and isomeric (C) nanoaggregates with the density functional theory method. We found that polarizability exaltation increases with the size of the nanostructure and originates from the response of the sp-hybridized carbon atoms to the external electric field. The highest contributions to the dipole polarizability of (C) and (C) come from the most remote atoms of the marginal fullerene cores. The sp-hybridized carbon atoms of cyclobutane bridges negligibly contribute to the molecular property. A similar major contribution to the molecular polarizability from the marginal atoms is observed for related carbon nanostructures isomeric to (C) (tubular fullerene and nanopeanut). Additionally, we discuss the analogy between the polarizability exaltation of covalently bonded (C) and the increase in the polarizability found in experiments on fullerene nanoclusters/films as compared with the isolated molecules.
极化率增强是（C）纳米结构的典型特征。它与（C）和C的平均极化率之比有关：前者高于原始富勒烯的 - 倍平均极化率。这种现象被用于新型富勒烯化合物的设计及其性质的理解，但仍缺乏化学合理性。在本工作中，我们用密度泛函理论方法研究了（C）和异构（C）纳米聚集体的分布极化率。我们发现极化率增强随纳米结构尺寸的增加而增加，并且源于sp杂化碳原子对外加电场的响应。（C）和（C）的偶极极化率的最大贡献来自边缘富勒烯核中最远端的原子。环丁烷桥的sp杂化碳原子对分子性质的贡献可忽略不计。对于与（C）异构的相关碳纳米结构（管状富勒烯和纳米花生），也观察到边缘原子对分子极化率有类似的主要贡献。此外，我们还讨论了共价键合的（C）的极化率增强与富勒烯纳米团簇/薄膜实验中与孤立分子相比发现的极化率增加之间的类比。
