Abstract
Ionic dissociation of nitromethane has been studied by means of H e(I) photoelectron—photoion coincidence spectroscopy and observation of metastable ions. The appearance energy of NO 2 + from CH 3NO 2 is close to the thermodynamic onset for CH 3 + NO 2 + while CH 3 + appears 1.2 eV above the onset for CH 3 + + NO 2. The breakdown curves and the kinetic energy releases indicate that CH 3 + formation would not yield the product of an electronic ground state, but rather accompanies an excitation of the NO 2 fragment. This process and NO + formation at higher ionization energies are not preceded by an internal conversion to the electronic ground state but occur from an isolated electronic state. The major fragmentations can be interpreted by the state correlation but not by the quasi-equilibrium theory.
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