期刊
SCIENCE
卷 306, 期 5699, 页码 1158-1161出版社
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1104386
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We present a combined experimental and theoretical investigation of formaldehyde (H2CO) dissociation to H-2 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 H-2. The second dissociation pathway yields rotationally cold CO in conjunction with highly vibrationally excited H-2. 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.
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