The Observation of CH3O in the Collision Free Multiphoton Dissociation of CH3NO2.
Abstract
The method of infra-red, laser, crossed, molecular-beam, photofragmentation, translational spectroscopy has been used to study the thermal chemistry of nitromethane under collision free conditions. We have observed for the first time experimental evidence that shows that the isomerization of nitromethane to methylnitrite is an important thermochemical process in the unimolecular decomposition of the title compound. Based on theoretical predictions of Dewar et.al. that the Arrhenius pre-exponential factor is 10 to the 13.3 power, we have been able to estimate the potential energy barrier height for the isomerization reaction to be 55.5 + or - 1.5 kcal/mol, compared to the C-N bond energy of 59.2 kcal/mol. It is clear that in mechanistic modeling of the thermal decomposition of nitromethane, this important dissociation channel must be taken into consideration. We have also been able to conclusively show that previous suggestions of a dynamical barrier in the exit channel of the simple C-N bond fission reaction are in error. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 24, 1985
- Accession Number
- ADA161420
Entities
People
- Alec M. Wodtke
- Eric J. Hintsa
- Yuan T. Lee
Organizations
- University of California, Berkeley