期刊
SCIENCE
卷 315, 期 5818, 页码 1561-1565出版社
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1136453
关键词
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资金
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0947071] Funding Source: National Science Foundation
Ion imaging reveals distinct photodissociation dynamics for propanal cations initially prepared in either the cis or gauche conformation, even though these isomers differ only slightly in energy and face a small interconversion barrier. The product kinetic energy distributions for the hydrogen atom elimination channels are bimodal, and the two peaks are readily assigned to propanoyl cation or hydroxyallyl cation coproducts. Ab initio multiple spawning dynamical calculations suggest that distinct ultrafast dynamics in the excited state deposit each conformer in isolated regions of the ground-state potential energy surface, and, from these distinct regions, conformer interconversion does not effectively compete with dissociation.
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