Abstract
AbstractCollision‐induced dissociation of nitromethane molecular ions to NO+ and NO has been studied at 19 eV center‐of‐mass collision energy using a crossed‐beam tandem mass spectrometer. Center‐of‐mass velocity contour maps for the two dissociation processes are distinctly different; NO has its intensity maximum at 7 degrees with energy transfer endothermicities of 1.8 eV while NO+ has intensity maxima at zero and 8 degrees with energy transfer endothermicities of 0.3 and 5.5 eV, respectively. The observation of two distinct peaks in the NO+ contour map clearly demonstrates that nitromethane ions excited to 5.5 eV internal energy do not dissociate from the ground state potential surface. Dissociation is faster than intramolecular relaxation, in contradiction to the fundamental postulate of statistical theories (RRKM, QET) for unimolecular dissociation.
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