Abstract

Ultrafast tunnel ionization enables femtosecond time-resolved dynamic measurements of the retro-Diels-Alder reactions of positively charged cyclohexene, norbornene, and dicyclopentadiene. Unlike the reaction times of 500-600ps that are observed following UV excitation of neutral species, on the ionic potential energy surfaces, these reactions occur on a single picosecond timescale and, in some cases, exhibit vibrational coherence. In the case of norbornene, a 270cm-1 vibrational mode is found to modulate the retro-Diels-Alder reaction.

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