Ohta Yasuhito, Okamoto Yoshiko, Irle Stephan, Morokuma Keiji
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan.
ACS Nano. 2008 Jul;2(7):1437-44. doi: 10.1021/nn8001906.
Continued growth of a single-walled carbon nanotube (SWNT) on an Fe cluster at 1500 K is demonstrated using quantum chemical molecular dynamics simulations based on the self-consistent-charge density-functional tight-binding (SCC-DFTB) method. In order to deal with charge transfer between carbon and metal particles and the multitude of electronic states, a finite electronic temperature approach is applied. We present trajectories of 45 ps length, where a continuous supply of carbon atoms is directed toward the C-Fe boundary between a 7.2 A long armchair (5,5) SWNT fragment and an attached Fe(38) cluster. The incident carbon atoms react readily at the C-Fe interface to form C- and C(2)-extensions on the tube rim that attach to the Fe cluster. These bridging sp-hybridized carbon fragments are vibrationally excited and highly mobile and, therefore, become engaged in frequent bond formation and breaking processes between their constituent C and the Fe atoms. The sp-hybridized carbon bridge dynamics and their reactions with the Fe-attached nanotube end bring about formations of new five-, six-, and seven-membered carbon rings extending the tube sidewall, resulting in overall continued growth of the nanotube on the Fe cluster up to nearly twice its length. Due to the random nature of new polygon formation, sidewall growth is observed as an irregular process without clear SWNT chirality preference. Compared to fullerene formation, heptagon formation is considerably promoted.
利用基于自洽电荷密度泛函紧束缚(SCC-DFTB)方法的量子化学分子动力学模拟,证明了在1500 K的铁簇上,单壁碳纳米管(SWNT)的持续生长。为了处理碳与金属颗粒之间的电荷转移以及众多电子态,应用了有限电子温度方法。我们展示了长度为45 ps的轨迹,其中碳原子持续供应到7.2 Å长的扶手椅型(5,5)SWNT片段与附着的Fe(38)簇之间的C-Fe边界。入射的碳原子在C-Fe界面处很容易发生反应,在管边缘形成C和C(2)延伸部分并附着到铁簇上。这些桥接的sp杂化碳片段被振动激发且高度移动,因此在其组成的C原子和Fe原子之间频繁参与键的形成和断裂过程。sp杂化碳桥的动力学及其与附着铁的纳米管末端的反应导致形成新的五元、六元和七元碳环,从而使纳米管侧壁延伸,导致纳米管在铁簇上整体持续生长至其长度的近两倍。由于新多边形形成的随机性,侧壁生长是一个不规则过程,没有明显的SWNT手性偏好。与富勒烯形成相比,七元环的形成得到了显著促进。