Accession Number : ADA298606

Title :   Simulation of the Vibrational Overtone Activation of Methylcyclopropene.

Descriptive Note : Technical rept.,

Corporate Author : BOWLING GREEN STATE UNIV OH CENTER FOR PHOTOCHEMICAL SCIENCES

Personal Author(s) : Ouporov, I. ; Snavely, D. L. ; Grinevich, O.

PDF Url : ADA298606

Report Date : 07 SEP 1995

Pagination or Media Count : 29

Abstract : The complete kinetic data for the vibrational overtone activation of methylcyclopropene have been simulated using a combination of master equation and Monte Carlo procedures. The simulation included photoactivation, collisional energy transfer and reaction into three unimolecular channels. A good fit to the Stern-Volmer plots for all the products at six different photolysis energies was obtained. The fit required an adjustment of the thermal activation barriers input into the RRKM calculation. The best fit barriers were: 12,833 cm-1 for 2-butyne, 14,547 cm-1 for 1,3-butadiene and 14,685 cm-1 for 1,2-butadiene. The collisional deactivation was fit with a single exponential energy transfer distribution function with an average amount of energy transferred per collision of 1000 cm-1. This average value fit all of the Stern-Volmer plots. The product yield ratios were examined for local mode specific effects, but none were found. Stem-Volmer plots were constructed for methyl cyclopropene diluted in helium, argon and sulfur hexafluoride for the Av = 6 olefinic CH stretch transition. These plots were simulated using the same calculation parameters as above except for those having to do with the collider gas. For these simulations the average amounts of energy transferred were 150, 200 and 500 cm-1 for helium, argon and sulfur hexafluoride, respectively. (AN)

Descriptors :   *MOLECULAR VIBRATION, *PROPENES, *PHOTOACTIVATION ANALYSIS, COMPUTERIZED SIMULATION, REACTION KINETICS, PHOTOCHEMICAL REACTIONS, PHOTOLYSIS, MOLECULAR STATES, ENERGY TRANSFER, MONTE CARLO METHOD, HELIUM, MOLECULE MOLECULE INTERACTIONS, ARGON, FLUORIDES, GAS CHROMATOGRAPHY, BUTADIENES, PARTICLE COLLISIONS, SULFUR COMPOUNDS, DEACTIVATION, ACTIVATION ENERGY.

Subject Categories : Organic Chemistry
      Radiation and Nuclear Chemistry
      Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE