论文标题
与过渡状态分叉的对称势能表面中选择性的相空间机制
The Phase Space Mechanism for Selectivity in a Symmetric Potential Energy Surface with a Post-Transition-State Bifurcation
论文作者
论文摘要
化学选择性是势能表面（PE）所显示的现象，该现象与许多有机化学反应相关，其PES在两个顺序索引-1鞍之间的区域中具有山谷 - ridge拐点（VRI）。在这封信中，我们描述了基本的动力学空间空间机制，该机制定性地确定了分叉反应途径产生的产物分布。我们表明，选择性是系统中存在的不稳定周期轨道（UPOS）家族之间不变的流形之间建立的杂智性和同型连接的结果。同型和异晶连接的几何形状使用拉格朗日描述符技术（一种基于轨迹的标量技术）确定，具有揭示表征传输的相位空间结构的几何模板的能力。
Chemical selectivity is a phenomenon displayed by potential energy surfaces (PES) that is relevant for many organic chemical reactions whose PES feature a valley-ridge inflection point (VRI) in the region between two sequential index-1 saddles. In this letter we describe the underlying dynamical phase space mechanism that qualitatively determines the product distributions resulting from bifurcating reaction pathways. We show that selectivity is a consequence of the heteroclinic and homoclinic connections established between the invariant manifolds of the families of unstable periodic orbits (UPOs) present in the system. The geometry of the homoclinic and heteroclininc connections is determined using the technique of Lagrangian descriptors, a trajectory-based scalar technique with the capability of unveiling the geometrical template of phase space structures that characterizes transport.
