Infrared Laser Photodetachment of Electrons from Vibrationally Excited Allyl Anions

Article abstract of DOI:10.1021/j150663a049

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, ?* = (6.5 +/- 2) x 1E-20 cm² at 945 cm^-1, using a low-power CW CO2 laser.The detachment yield decreases with increasing photon energy in the range 900-1100 cm^-1.Photodetachment from vibrationally relaxed anions also occurs but whit a much lower cross section, ? = (6.3 +/- 3) x 1E-23 cm².When fluoride ion reacts with allyltrimethylsilane, about 30percent of the nascent allyl anions are vibrationally excited.The predominant relaxation mechanism below 1E-6 torr is radiative emission with a measured rate constant of 53 +/- 10 s^-1.