Irle Stephan, Zheng Guishan, Wang Zhi, Morokuma Keiji
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
J Phys Chem B. 2006 Aug 3;110(30):14531-45. doi: 10.1021/jp061173z.
The dynamic self-assembly mechanism of fullerene molecules is an irreversible process emerging naturally under the nonequilibrium conditions of hot carbon vapor and is a consequence of the interplay between the dynamics and chemistry of polyyne chains, pi-conjugation and corresponding stabilization, and the dynamics of hot giant fullerene cages. In this feature article we briefly present an overview of experimental findings and past attempts to explain fullerene formation and show in detail how our recent quantum chemical molecular dynamics simulations of the dynamics of carbon vapor far from thermodynamic equilibrium have assisted in the discovery of the combined size-up/size-down "shrinking hot giant" road that leads to the formation of buckminsterfullerene C60, C70, and larger fullerenes. This formation mechanism is the first reported case of order created out of chaos where a distinct covalent bond network of an entire molecule is spontaneously self-assembled to a highly symmetric structure and fully explains the fullerene formation process consistently with all available experimental observations a priori. Experimental evidence suggests that it applies universally to all fullerene formation processes irrespective of the carbon source.
富勒烯分子的动态自组装机制是在热碳蒸气的非平衡条件下自然出现的不可逆过程，是聚炔链的动力学与化学、π共轭及相应的稳定性以及热巨型富勒烯笼的动力学之间相互作用的结果。在这篇专题文章中，我们简要概述了实验发现以及过去解释富勒烯形成的尝试，并详细展示了我们最近对远离热力学平衡的碳蒸气动力学进行的量子化学分子动力学模拟，是如何助力发现导致巴基球C60、C70及更大富勒烯形成的“收缩热巨型分子”这种组合式放大/缩小路径的。这种形成机制是首次报道的从混沌中产生有序的案例，其中整个分子独特的共价键网络自发地自组装成高度对称的结构，并且与所有现有的先验实验观察结果一致，全面解释了富勒烯的形成过程。实验证据表明，无论碳源如何，该机制普遍适用于所有富勒烯的形成过程。
