Chemical Laser Studies of Energy Partitioning in Photochemical and Unimolecular Reactions.

摘要

Chemical laser techniques have been used to analyze energy partitioning and reaction dynamics in photochemical and unimolecular reactions which yield vibrationally excited hydrogen halide products. Six new unimolecular reaction chemical lasers and fifteen new photochemical lasers have been discovered. A general method for the quantitative determination of product vibrational state distributions has been developed and applied to many of the new lasers in addition to well-known chemical laser systems. Patterns of energy partitioning in first-order reactions reveal highly non-statistical behavior: (a) lasing hydrogen halide products have greater than a statistical allotment of reaction exoergicity and (b) decomposition of some unimolecular and photochemical reactants occurs in a 'non-RRKM'fashion. A non-statistical dynamical model has been formulated for energy partitioning into chemical reaction products;the model is in good accord with experimental results.