A Photoelectron Spectroscopic Study of the Ground States of CH2F+ and CD2F+

Article abstract of DOI:10.1021/j150655a036

The fluorine atom/methyl fluoride reaction has been studied by photoelectron spectroscopy.A new product band with vibrational components at 9.04 +/- 0.01 eV adiabatic and 9.22 +/- 0.01 eV vertical ionization energies is assigned to the CH2F free radical.The ν'= 0-1 vibronic separation measured as 1450 +/- 30 cm^-1 is due to the C-F stretching fundamental of the ground state of CH2F⁺; this vibronic interval was 1530 +/- 30 cm^-1 for CD2F⁺.The positive deuterium shift for CH2F⁺ is due to interaction with the H-C-H bending mode, which shifts below the C-F stretching mode on deuteration.The substantial increase in the C-F stretching modes for CH2F⁺ and CD2F⁺, as compared to 1163- and 1193-cm^-1 values for the CH2F and CD2F free radicals in solid argon, respectively, is due to increased net C-F bonding in the cations.