Sinitsa Alexander S, Polynskaya Yulia G, Matsokin Nikita A, Kedalo Yegor M, Knizhnik Andrey A, Popov Andrey M
Kintech Lab Ltd., 3rd Khoroshevskaya Street 12, Moscow 123298, Russia.
National Research Centre "Kurchatov Institute", Kurchatov Square 1, Moscow 123182, Russia.
Phys Chem Chem Phys. 2024 Aug 14;26(32):21905-21911. doi: 10.1039/d4cp02490g.
The disappearance of sp structural defects during abundant fullerene isomer formation is considered within the framework of the atomistic mechanism with participation of carbon atoms with sp hybridization. The study is carried out using the example of the icosahedral C- fullerene formation from the appropriate C- fullerene with a 7-ring. In this case the studied atomistic mechanism includes the following stages: (1) insertion of single carbon atoms into the fullerene from carbon vapor as an sp-atom instead of or above a bond, (2) directional migration of the sp-atom positions towards the 7-ring with decrease of energy, and (3) meeting of two sp atoms near the 7-ring with annihilation of the sp-atom pair and formation of the sp structure of the C- fullerene. The probabilities of all possible sp-atom positions on the appropriate C- fullerene shell are estimated as a function of temperature using the total energies of these positions obtained by spin-polarized density functional theory calculations using the PBE functional. Based on these estimations, it is shown that formation of the C- isomer is the most probable within the framework of the considered mechanism relative to other C isomers. The energetics of sp-atom pair annihilation in the formation of the C- isomer is also studied DFT calculations. The advantages of the considered atomistic mechanism of the abundant fullerene isomer formation are discussed.
在富勒烯异构体大量形成过程中sp结构缺陷的消失是在具有sp杂化碳原子参与的原子机制框架内进行考虑的。该研究以由具有7环的适当C - 富勒烯形成二十面体C - 富勒烯为例展开。在这种情况下，所研究的原子机制包括以下阶段：(1) 单个碳原子以sp原子的形式从碳蒸气中插入到富勒烯中，取代一个键或在键之上；(2) sp原子位置随着能量降低向7环定向迁移；(3) 两个sp原子在7环附近相遇，sp原子对湮灭并形成C - 富勒烯的sp结构。利用采用PBE泛函通过自旋极化密度泛函理论计算得到的这些位置的总能量，估计了适当C - 富勒烯壳上所有可能的sp原子位置的概率随温度的变化。基于这些估计结果表明，在所考虑的机制框架内，相对于其他C异构体，C - 异构体的形成是最有可能的。还通过DFT计算研究了C - 异构体形成过程中sp原子对湮灭的能量学。讨论了所考虑的富勒烯异构体大量形成的原子机制的优点。
