Dynamical Effects and Product Distributions in Simulated CN + Methane Reactions

Thomas J Preston, Balázs Hornung, Shubhrangshu Pandit, Jeremy N Harvey, Andrew J Orr-Ewing

Research output: Contribution to journalArticle (Academic Journal)peer-review

5 Citations (Scopus)
303 Downloads (Pure)

Abstract

Dynamics of collisions between structured molecular species quickly become complex as molecules become large. Reactions of methane with halogen and oxygen atoms serve as model systems for polyatomic molecule chemical dynamics, and replacing the atomic reagent with a diatomic radical affords further insights. A new, full-dimensional potential energy surface for collisions between CN + CH4 to form HCN + CH3 is developed and then used to perform quasi-classical simulations of the reaction. Coupled-cluster energies serve as input to an empirical valence bonding (EVB) model, which provides an analytical function for the surface. Efficient sampling permits simulation of velocity-map ion images and exploration of dynamics over a range of collision energies. Reaction populates HCN vibration, and energy partitioning changes with collision energy. The reaction cross-section depends on the orientation of the diatomic CN radical. A two-dimensional extension of the cone of acceptance for an atom in the line-of-centers model appropriately describes its reactivity. The simulation results foster future experiments and diatomic extensions to existing atomic models of chemical collisions and reaction dynamics.
Original languageEnglish
Pages (from-to)4672–4682
Number of pages11
JournalJournal of Physical Chemistry A
Volume120
Issue number27
Early online date26 Jan 2016
DOIs
Publication statusPublished - 14 Jul 2016

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