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Updated: Jul 15, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Photodissociation dynamics of the 2-propyl radical, C3H7
1Institute of Physical Chemistry, University of Würzburg, Am Hubland D-97074 Würzburg, Germany.
Abstract:
The photodissociation of 2-propyl leading to propene+H was investigated with nanosecond time resolution. A supersonic beam of isolated 2-propyl radicals was produced by pyrolysis of 2-bromopopane. The kinetic energy release of the H-atom photofragment was monitored as a function of excitation wavelength by photofragment Doppler spectroscopy via the Lyman-alpha transition. The loss of hydrogen atoms after excitation proceeds in alpha position to the radical center with a rate constant of 5.8x10(7) s-1 at 254 nm. Approximately 20% of the excess energy is deposited as translation in the H-atom photofragment. In contrast 1-propyl does not lose H atoms to a significant extent. The experimental results are compared to simple Rice-Ramsperger-Kassel-Marcus calculations. The possible reaction pathways are examined in hybrid density functional theory calculations.
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