Activation Energies and Beyond

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2019-08, Vol.123 (33), p.7185-7194
• Main Authors: Piskulich, Zeke A, Mesele, Oluwaseun O, Thompson, Ward H
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.9b03967

Recent advances in the calculation and interpretation of the activation energy for a dynamical process are described. Specifically, new approaches that apply the fluctuation theory of statistical mechanics to dynamics enable the direct determination of the activation energy for an arbitrary dynamical time scale from simulations at a single temperature. This opens up significant new possibilities for understanding activated processes in cases where a traditional Arrhenius analysis is not possible. The methods also enable a rigorous decomposition of the activation energy into contributions associated with the different interactions and motions present in the system. These components can be understood in the context of Tolman’s interpretation of the activation energy. Specifically, they provide insight into how energy can be most effectively deposited to accelerate the dynamics of interest, promising important new mechanistic information for a broad range of chemical processes. The general approach can be extended beyond activation energies to the examination of non-Arrhenius behavior as well as the changes in dynamical time scales with respect to other thermodynamic variables such as pressure.