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Bonn 2025 – wissenschaftliches Programm

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A: Fachverband Atomphysik

A 40: Cluster and Nanoparticles II (joint session MO/A)

A 40.3: Vortrag

Freitag, 14. März 2025, 11:45–12:00, HS XV

Insights into Facile Methane Activation by Transition Metal Ions via Intersystem CrossingMarcel Meta, Maximilian Huber, •Maurice Birk, Martin Wedele, Boris Heeb, and Jennifer Meyer — RPTU Kaiserslautern-Landau, Fachbereich Chemie und Landesforschungszentrum OPTIMAS, Kaiserslautern, Germany

A model for processes like single atom catalysis can be the study of isolated transition metal ion molecule reactions in the gas phase [1,2]. Here, we present a study of kinetics and dynamics on the activation of methane (CH4) by transition metal cations M++CH4 → MCH2++H2. The nominally spin-forbidden reaction requires intersystem crossing (ISC) to proceed. The impact of ISC on the dynamics is studied by collaborative effort combining experiment and theory.
We used crossed-beam velocity map imaging to measure differential cross sections for the carbene formation in the reaction with tantalum Ta+ [3]. The reaction shows dominantly indirect dynamics which is associated to the formation of a long-lived intermediate complex. Experiments for Ta+ are furthermore complemented by the reaction of CH4 with zirconium Zr+. In addition recent preliminary theoretical studies confirmed our observations regarding the reaction with Ta+ and also revealed that the bottleneck of this reaction is ISC between the quintet and triplet states.
[1] D. K. Böhme, H. Schwarz, Angew. Chem. Int. Ed. 2005, 44, 2336; [2] H. Schwarz, Catal. Sci. Tech. 2017, 7, 4302; [3] M. Meta, Faraday Discuss. 2024, 251, 587

Keywords: Crossed-Beams; Velocity Map Imaging; Methane; Tantalum; Zirconium

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