Determination of the energy distribution in unimolecular reactions under soft collision conditions

✍ Scribed by Juan M. Figuera; Vicente Menéndez; Juan C. Rodríguez

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 400 KB
• Volume: 17
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550170604

✦ Synopsis

The effective energy distribution of activated molecules at the time of reaction under soft collision conditions f ' ( E , w ) is pressure dependent and therefore difficult to recover from unimolecular decomposition data obtained a t different pressures. We show in this work that the part of this function restricted to the condition that the collision frequency w has to be equal to the microscopic rate constant k(E) a t the energy given f " [ E , w = k(E)1 is a reasonable approximation to the input energy distribution f ( E ) for quite soft collisions. This function is not pressure dependent and then recoverable at least in principle and as a matter of fact is not conceptually far from the function that the already reported deconvolution methods based in physical approximations attempt to recover. The deconvolution methods have been checked under soft collision conditions. We have found that the input energy distribution is recovered with reasonable accuracy for energies transferred by collision (AE) above 5 kcal mol-', conditions common in polyatomic systems.