Journal
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 62
Volume 62, Issue -, Pages 531-553Publisher
ANNUAL REVIEWS
DOI: 10.1146/annurev-physchem-032210-103518
Keywords
reaction dynamics; roaming pathway; global potential energy surfaces; photodissociation dynamics; transition-state theory
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Roaming is a recently verified unusual pathway to molecular products from unimolecular dissociation of an energized molecule. Here we present the evidence for this pathway for H2CO and CH3CHO. Theoretical analysis shows that this path visits the plateau region of the potential energy surface near dissociation to radical products. It is not clear whether roaming is a distinct isolated pathway, in addition to the conventional one via the well-known molecular saddle-point transition state. Evidence is presented to suggest that the two pathways may originate from a single, but highly complicated, dividing surface. Other examples of unusual reaction dynamics are also reviewed.
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