Energy Distributions in Unimolecular Reactions

Abstract

AbstractThe present paper describes results on modes of anharmonically coupled oscillators in a molecule, the role of energy exchange and neardegeneracy, and quasi‐periodic versus ergodic theory of unimolecular reactions. The quasi‐periodic one is a formal generalization of Slater's harmonic oscillator theory. Spectral decomposition of a classical trajectory for the molecule provides insight into the molecular spectrum, both in the low (quasi‐periodic) and high (ergodic) energy regimes. The role of quantization of transition states in unimolecular reactions and a relation to vibrational adiabaticity are analyzed. Results obtained on energy distribution of translational energy of molecular beam reactions involving, intermediate complexes and tight exit channel transition states are described together with the relation to intramolecular energy randomization.