乙炔高温裂解的从头算动力学模拟

本文采用了从头算动力学结合量化计算来研究乙炔的热裂解，发现了一条通过连续乙烯基卡宾加成生成苯环的机理，并和与这条路径相竞争的路径进行了对比. 此外，还得到了乙烯基卡宾的寿命.

Unexpected Chemistry from the Homogeneous Thermal Decomposition of Acetylene: An ab initio Study

The formation of the aromatic ring during the formation of polycyclic aromatic hydrocarbons (PAHs) remains controversial and the experimental evidence is still lacking. Moreover, the formation mechanism of benzene from acetylene in the gas phase has also puzzled organic chemists for decades. Here, ab initio molecular dynamics simulations and electronic structure calculations provide compelling evidence for an unexpected competitive reaction pathway in which the aromatic ring is formed through successive additions of vinylidene. Moreover, no collisions cause bond dissociation of the acetylene molecule during the formation of benzene in this work. This study reveals the key role for the vinylidene carbene and determines the lifetime of vinylidene.