期刊
SCIENCE
卷 325, 期 5938, 页码 303-306出版社
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1175018
关键词
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资金
- National Science Council of Taiwan
- Academia Sinica
- Air Force Office of Scientific Research [AOARD-09-4030]
Most studies of the impact of vibrational excitation on molecular reactivity have focused on reactions with a late barrier (that is, a transition state resembling the products). For an early barrier reaction, conventional wisdom predicts that a reactant's vibration should not couple efficiently to the reaction coordinate and thus should have little impact on the outcome. We report here an in-depth experimental study of the reactivity effects exerted by reactant C-H stretching excitation in a prototypical early-barrier reaction, F + CHD3. Rather counterintuitively, we find that the vibration hinders the overall reaction rate, inhibits scission of the excited bond itself (favoring the DF + CHD2 product channel), and influences the coproduct vibrational distribution despite being conserved in the CHD2 product. The results highlight substantial gaps in our predictive framework for state-selective polyatomic reactivity.
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