Ong Mitchell T, Leiding Jeff, Tao Hongli, Virshup Aaron M, Martínez Todd J
Department of Chemistry, Stanford University, Stanford, California 94305, USA.
J Am Chem Soc. 2009 May 13;131(18):6377-9. doi: 10.1021/ja8095834.
We use ab initio steered molecular dynamics to investigate the mechanically induced ring opening of cyclobutene. We show that the dynamical results can be considered in terms of a force-modified potential energy surface (FMPES). We show how the minimal energy paths for the two possible competing conrotatory and disrotatory ring-opening reactions are affected by external force. We also locate minimal energy pathways in the presence of applied external force and show that the reactant, product, and transition state geometries are altered by the application of external force. The largest effects are on the transition state geometries and barrier heights. Our results provide a framework for future investigations of the role of external force on chemical reactivity.
我们使用从头算引导分子动力学来研究机械诱导的环丁烯开环反应。我们表明，动力学结果可以通过力修正势能面（FMPES）来考虑。我们展示了外部力如何影响两种可能的竞争顺旋和对旋开环反应的最小能量路径。我们还确定了在有外部力作用时的最小能量路径，并表明反应物、产物和过渡态的几何结构会因外部力的作用而改变。最大的影响在于过渡态的几何结构和势垒高度。我们的结果为未来研究外力对化学反应性的作用提供了一个框架。
