CHAPTER 10: Cold Ion Chemistry
Published:06 Dec 2017
D. Zhang and S. Willitsch, in Cold Chemistry: Molecular Scattering and Reactivity Near Absolute Zero, ed. O. Dulieu and A. Osterwalder, The Royal Society of Chemistry, 2017, pp. 496-536.
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Studying chemical reactions at very low temperatures is of importance for the understanding of fundamental physical and chemical processes. At very low energies, collisions are dominated by only a few partial waves. Thus, studies in this regime allow the characterization of quantum effects which depend on the collisional angular momentum, e.g., reactive scattering resonances and tunneling through centrifugal barriers. Additionally, the dynamics of ultralow-energy collisions is dominated by long-range interactions, i.e., “universal” chemical forces. Thus, experiments in this domain probe the details of intermolecular interactions which is of general relevance for the understanding of chemical processes. Moreover, the increasingly more precise experiments provide valuable data for benchmarking theoretical models and quantum chemical calculations. Studies of cold ion–neutral reactions in the laboratory rely on techniques for the generation of cold ions and cold neutrals. Over the last decades, the technology in this domain has made impressive progress. Many of these techniques allow not only the translational cooling of the molecules, but also a precise preparation of their internal quantum state. Thus, by an accurate preparation of both the energy and state of the reaction partners as well as by the application of external electric, magnetic or optical fields, prospects open up to study and control chemical processes at an unprecedented level of accuracy. In this chapter, we review salient theoretical concepts and recent experimental developments for studies of ion–molecule reactions at low temperatures. We first discuss the theoretical background for the description of low-energy ion–molecule reactions. Next we present key experimental methods for laboratory studies of cold ion–molecule reactions. The chapter concludes with a review of illustrative results and an outlook on future directions.