First Principles Dynamics and Minimum Energy Pathways for Mechanochemical Ring Opening of Cyclobutene
First Principles Dynamics and Minimum Energy Pathways for Mechanochemical Ring Opening of Cyclobutene
复制标题
DOI：
10.1021/ja8095834
复制
发表时间：
2009-05-13
影响因子：
15
通讯作者：
Martinez, Todd J.
中科院分区：
文献类型：
--
作者：
Ong, Mitchell T.;Leiding, Jeff;Martinez, Todd J.
我们用从头算分子动力学方法研究了环丁烯的机械诱导开环反应。我们证明了动力学结果可以用力修正势能面(FMPES)来考虑。我们展示了外力如何影响两个可能竞争的旋转和不旋转开环反应的最小能量路径。我们还找到了在外力存在时的最小能量路径，并表明外力的作用改变了反应物、产物和过渡态的几何形状。影响最大的是过渡态几何形状和势垒高度。我们的结果为未来研究外力对化学反应的作用提供了一个框架。
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.