CHAPTER 5: Rate Constants, Cross Sections and Reactive Scattering

This chapter discusses rate constants and their relationship to cross sections. The concept of a detailed state-to-state rate constant is introduced and the ground-breaking experiments of John Polanyi, in which such rate constants were measured for the first time, are discussed. The “cumulative reaction probability” is introduced and the “detailed balance” relationship of forward and backward reaction rate constants is expounded. The chapter goes on to discuss the experimental measurement of reaction cross sections using crossed molecular beam experiments starting from a historical perspective and then presenting the most versatile modern methodology.