Phase Space Structures Explain Hydrogen Atom Roaming in Formaldehyde Decomposition
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- 作者：Fr茅d茅ric A. L. Maugui猫re ; Peter Collins ; Zeb C. Kramer ; Barry K. Carpenter ; Gregory S. Ezra ; Stavros C. Farantos ; Stephen Wiggins
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2015
- 出版时间：October 15, 2015
- 年：2015
- 卷：6
- 期：20
- 页码：4123-4128
- 全文大小：411K
- ISSN：1948-7185
文摘
We re-examine the prototypical roaming reaction鈥攈ydrogen atom roaming in formaldehyde decomposition鈥攆rom a phase space perspective. Specifically, we address the question 鈥渨hy do trajectories roam, rather than dissociate through the radical channel?鈥?We describe and compute the phase space structures that define and control all possible reactive events for this reaction, as well as provide a dynamically exact description of the roaming region in phase space. Using these phase space constructs, we show that in the roaming region, there is an unstable periodic orbit whose stable and unstable manifolds define a conduit that both encompasses all roaming trajectories exiting the formaldehyde well and shepherds them toward the H2路路路CO well.