Consecutive reactions of small, free tantalum clusters with dioxygen controlled by relaxation dynamics.
The reaction of small cationic tantalum clusters (Tan+, n = 4-8) with molecular oxygen is studied under multi-collision conditions in the gas phase, and the reaction kinetics are analyzed in order to elucidate underlying mechanisms. Reaction pathways as well as relevant apparent rate constants are reported. Two principal pathways in the consecutive oxidation reaction are present in this size regime: solely oxidative degradation (loss of a TaO fragment) in the beginning followed by parallel intact oxidation of certain intermediate species. Selected product structures and energies are subsequently determined via density functional theory calculations. The branching between oxidative fragmentation and intact oxidation is related to the corresponding relaxation dynamics.
Lehrstuhl für Physikalische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany. tschurl@tum.de.
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JF
Eckhard
Lehrstuhl für Physikalische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany. tschurl@tum.de.
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Neuwirth
Lehrstuhl für Theoretische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany.
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Panosetti
Lehrstuhl für Theoretische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany.
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Oberhofer
Lehrstuhl für Theoretische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany.
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K
Reuter
Lehrstuhl für Physikalische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany. tschurl@tum.de.
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http://orcid.org/0000-0001-6618-7312
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Tschurl
Lehrstuhl für Physikalische Chemie, Chemistry Department & Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany. tschurl@tum.de.
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Heiz