Vib-Rotational Energy Transfer and Relaxation Patterns in Non-Equilibrium Chemical Systems

摘要

The characteristics of vibrational relaxation of diatomic molecules are analyzed using a combined kinetic-thermodynamic approach based on the master equation formalism on the one hand and the maximal entropy procedure on the other. The complex and detailed solutions for the vibrational relaxation of diatomic molecules (HF as a specific system) can be greatly compacted and systemized. The physical-mathematical significance of detailed balancing and quasi-equilibrium distributions in non-isothermal systems are discussed. It is shown that the increased efficiency of rotationally relaxed chemical lasers is due to the removal of thermodynamic constraints from the molecular distribution function. The different roles of reagent internal excitation on the rates of endoergic reactions at a given temperature and a given total energy are discussed and demonstrated. (Author)