Sigma bond activation of deuterium mediated by atomic cerium cations: Experiment and theory
Autor: | Paul R. Kemper, Rusty Trainham, Manuel J. Manard, P. B. Armentrout |
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Rok vydání: | 2019 |
Předmět: |
Exothermic reaction
010401 analytical chemistry chemistry.chemical_element Electronic structure 010402 general chemistry Condensed Matter Physics 01 natural sciences 0104 chemical sciences Cerium chemistry.chemical_compound Reaction rate constant chemistry Deuterium Insertion reaction Physical chemistry Density functional theory Physical and Theoretical Chemistry Sigma bond Instrumentation Spectroscopy |
Zdroj: | International Journal of Mass Spectrometry. 441:19-24 |
ISSN: | 1387-3806 |
Popis: | Reaction of ground-state Ce+ (5d24f1) with deuterium in a reaction cell at a pressure of 1.5–4.0 Torr and temperatures ranging from approximately 265–515 K is studied. Rate constants for formation of CeD2+ are acquired and vary from approximately 2.8 × 10−14 to 2.1 × 10−13 cm3/s. A negative temperature dependence is observed for the measured rate constants, indicating the reaction becomes less efficient as the temperature increases, consistent with an exothermic reaction. Electronic structure calculations were performed using density functional theory (DFT) at the PBE0 level to characterize all reactant and product species as well as to generate potential energy surfaces (PESs) for the insertion reaction. This combination of experimental and theoretical results suggest that Ce+ inserts into the deuterium sigma bond in an overall exothermic and barrierless process. |
Databáze: | OpenAIRE |
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