Chemical kinetics and diffusion approach: the history of the Klein-Kramers equation (Q610708)

The author reviews the theoretical development of the stochastic diffusion approach to describing quantitative aspects of chemical reactions in the first half of the twentieth century. This is done with the particular goal to provide historical and methodological reasons why the diffusive approach was underestimated and education and research has almost exclusively focused on the transition state theory (TST) for many years. Based on the fundamental works of Albert Einstein and Marian von Smoluchowski on the theory of Brownian motion and random walks, Jens Anton Christiansen, Oskar Benjamin Klein and Hendrik Anton Kramers were key researchers who elaborated the diffusive description of chemical kinetics. Unfortunately, due to historical and personal reasons, they were not successful in popularizing it widely, although it has a number of advantages in comparison with TST. Moreover, the diffusive stochastic approach requires more profound expertise in mathematics and physics from possible applicants than TST and gives less predictive results. Besides its contributions to the history of mathematics and chemistry, the article transfers the decisive results, in particular the derivation of the Klein-Kramers equation and the ``gems'' from \textit{H. A. Kramers}' paper [Physica 7, 284--304 (1940; Zbl 0061.46405)] in 1940, into modern terminology and notation, thereby making them easily accessible to new generations of researchers in the field.