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Published September 1, 1984 | metadata_only
Journal Article

Infrared laser photodetachment of electrons from vibrationally excited allyl anions


Infrared laser photodetachment of allyl anions has been investigated using the techniques of ion cyclotron resonance (ICR) spectroscopy. Facile detachment of vibrationally excited anions occurs with a phenomenologically defined cross section, σ* = (6.5 ± 2) X 10^(-20) cm^2 at 945 cm^(-1), using a low-power CW CO_2 laser. The detachment yield decreases with increasing photon energy in the range 900-1100 cm^(-1). Photodetachment from vibrationally relaxed anions also occurs but with a much lower cross section, σ = (6.3 ± 3) X 10^(-23) cm^2. When fluoride ion reacts with allyltrimethylsilane, about 30% of the nascent allyl anions are vibrationally excited. The predominant relaxation mechanism below 10^(-6) torr is radiative emission with a measured rate constant of 53 ± 10 s^(-1).

Additional Information

© 1984 American Chemical Society. Received: November 4, 1983; In Final Form: March 13, 1984. We thank the reviewer for helpful comments and Dr. B. S. Ault for providing the sample of NF_3. This work is supported in part by the President's Fund of the California Institute of Technology and by the U.S. Department of Energy.

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August 19, 2023
August 19, 2023