Development of Microcanonical Statistical Rate Theory for Unimolecular Reactions

Abstract

This chapter reviews the development of the statistical rate theory including the recent proposal for its further improvement, with emphasis on the development of microcanonical features. Since the birth of the statistical rate theory in the 1930s, a tremendous number of experiments have been conducted to prove the adequacy or inadequacy of the statistical treatment. The chapter discusses the fundamental assumptions originally embedded in the statistical rate theory. It summarizes the fundamental assumptions originally embedded in the statistical rate theory. The chapter describes both the canonical transition state theory and the microcanonical RRKM theory for unimolecular reactions. Typical restrictions that are due to the adiabaticity of the quantum state, incomplete energy randomization, and the vectorial correlation reflecting the shape of potential energy surface. The chapter also reviews the product energy distribution is another important element of chemical reactions and, of course, closely related to the statistical rate theory.