Resonances in the Entrance Channel of the Elementary Chemical Reaction of Fluorine and Methane

Extending the fully quantum‐state‐resolved description of elementary chemical reactions beyond three or four atom systems is a crucial issue in fundamental chemical research. Reactions of methane with F, Cl, H or O are key examples that have been studied prominently. In particular, reactive resonances and nonintuitive mode‐selective chemistry have been reported in experimental studies for the F+CH4→HF+CH3 reaction. By investigating this reaction using transition‐state spectroscopy, this joint theoretical and experimental study provides a clear picture of resonances in the F+CH4 system. This picture is deduced from high‐resolution slow electron velocity‐map imaging (SEVI) spectra and accurate full‐dimensional (12D) quantum dynamics simulations in the picosecond regime. Chemische Reaktivität: Experimentelle und theoretische Daten zeigen übereinstimmend das Vorhandensein von mittels Übergangszustands‐Spektroskopie bestimmten Resonanzen im Eintrittskanal der Reaktion F+CH4→HF+CH3 (siehe Bild; ΔSO=atomare Spin‐Bahn‐Kopplung). Volldimensionale Quantendynamikrechnungen geben ein klares Bild und erklären das Auftreten der Resonanzen.