The roaming atom: straying from the reaction path in formaldehyde decomposition.

Townsend, D; Lahankar, S A; Lee, S K; Chambreau, S D; Suits, A G; Zhang, X; Rheinecker, J; Harding, L B et al. · Science · 2004

basic_science · Level V

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Abstract

We present a combined experimental and theoretical investigation of formaldehyde (H2CO) dissociation to H2 and CO at energies just above the threshold for competing H elimination. High-resolution state-resolved imaging measurements of the CO velocity distributions reveal two dissociation pathways. The first proceeds through a well-established transition state to produce rotationally excited CO and vibrationally cold H2. The second dissociation pathway yields rotationally cold CO in conjunction with highly vibrationally excited H2. Quasi-classical trajectory calculations performed on a global potential energy surface for H2CO suggest that this second channel represents an intramolecular hydrogen abstraction mechanism: One hydrogen atom explores large regions of the potential energy surface before bonding with the second H atom, bypassing the saddle point entirely.