Phase space structures explain hydrogen atom roaming in formaldehyde decomposition

Mauguiere, Frederic A. L., Collins, Peter, Kramer, Zeb C., Carpenter, Barry K. ORCID: https://orcid.org/0000-0002-5470-0278, Ezra, Gregory S., Farantos, Stavros C. and Wiggins, Stephen 2015. Phase space structures explain hydrogen atom roaming in formaldehyde decomposition. Journal of Physical Chemistry Letters 6 (20) , pp. 4123-4128. 10.1021/acs.jpclett.5b01930

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Abstract

We re-examine the prototypical roaming reaction—hydrogen atom roaming in formaldehyde decomposition—from a phase space perspective. Specifically, we address the question “why do trajectories roam, rather than dissociate through the radical channel?” 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···CO well.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	American Chemical Society
ISSN:	1948-7185
Funders:	NSF/EPSRC
Date of First Compliant Deposit:	19 October 2018
Date of Acceptance:	1 October 2015
Last Modified:	05 May 2023 06:32
URI:	https://orca.cardiff.ac.uk/id/eprint/77647

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