Capture theory models: An overview of their development, experimental verification, and applications to ion–molecule reactions

Journal article

Since Arrhenius first proposed an equation to account for the behavior of thermally activated reactions in 1889, significant progress has been made in our understanding of chemical reactivity. A number of capture theory models have been developed over the past several decades to predict the rate coefficients for reactions between ions and molecules-ranging from the Langevin equation (for reactions between ions and non-polar molecules) to more recent fully quantum theories (for reactions at ultracold temperatures). A number of different capture theory methods are discussed, with the key assumptions underpinning each approach clearly set out. The strengths and limitations of these capture theory methods are examined through detailed comparisons between low-temperature experimental measurements and capture theory predictions. Guidance is provided on the selection of an appropriate capture theory method for a given class of ion-molecule reaction and set of experimental conditions-identifying when a capture-based model is likely to provide an accurate prediction. Finally, the impact of capture theories on fields such as astrochemical modeling is noted, with some potential future directions of capture-based approaches outlined.

Authors: Tsikritea, A; Diprose, JA; Softley, TP; Heazlewood, BR

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Institute of Physics
• Journal: The Journal of Chemical Physics
• Volume: 157
• Issue: 6
• Pages: 060901-060901
• Article number: 060901
• Publication date: 2022-06-23
• DOI: 10.1063/5.0098552
• EISSN: 1089-7690
• ISSN: 0021-9606
• Language: English
• Keywords: Statistical physics; Quantum mechanics; Set (abstract data type); Reaction rate constant; Arrhenius equation; Computer science; Transition state theory; Molecule; Chemistry; Ion; Physics; Physical chemistry; Computational chemistry