D. Talbi, D.J. Defrees, et al.
ApJ
We have measured the photoelectron spectra of CH2CN- and CD2CN- and report the following electron affinities: EA(CH2CN) = 1.543 ± 0.014 eV and EA(CD2CN) = 1.538 ± 0.012 eV. From an analysis of the peak splittings and intensities, we extract potential-energy curves for the umbrella mode of the CH2CN- negative ion and the CH2CN radical. The radical is found to be a planar, C2ν, species. The structure of the cyanomethide ion is almost described as CH2=C=N-, but the hydrogens are bent slightly out of the molecular plane. A Franck-Condon analysis leads to a value of the out-of-plane deformation angle as 30 ± 5° with a very small inversion barrier of 100 ± 50 cm-1. Our structural conclusions are reinforced by a series of ab initio Hartree—Fock and M⊘ller-Plesset perturbation calculations on both the cyanomethyl radical and cyanomethide ion. Using the gas-phase acidity of CH3CN, we obtain the following bond-dissociation energy for acetonitrile: DH°298(H-CH2CN) = 94.2 ± 2.0 kcal/mol. © 1987, American Chemical Society. All rights reserved.
D. Talbi, D.J. Defrees, et al.
ApJ
D.J. Defrees, A.D. McLean
Chemical Physics Letters
D.J. Defrees, J.S. Binkley, et al.
The Journal of Chemical Physics
Sean Moran, H. Benton Ellis, et al.
JACS