The effect of vibrational and translational energies of ionic reactant on the reaction NO++iso-C4H10→HNO+C4H+9

Abstract

The effect of vibrational energy of the ionic reactant on the rate of the reaction NO⁺+iso‐C₄H₁₀→HNO+C₄H⁺₉ has been examined by directly determining the relative reaction cross sections for the individual vibrational states from v=0 to 4. The reactant ions were produced by photoionization at suitable wavelengths and the relative abundances of the ions in various vibrational states were determined at each wavelength by photoelectron spectrometry. The translational energy dependence of the individual cross sections has also been studied by changing the repeller voltage in the ionization chamber. The cross section slightly decreased with increasing vibrational energy at lower relative kinetic energies, but it was almost constant within the experimental error at higher relative kinetic energies. The result has been explained in terms of the two‐mechanism model, viz., complex formation predominating at lower relative kinetic energies and stripping predominating at higher relative kinetic energies. Photoelectron spectra of NO taken at 133.6, 127.7, 122.9, 120.5, and 117.6 nm are also presented.