Dataset Information

Reaction of Ta₃ ^- Clusters with Molecular Nitrogen: A Mechanism Investigation.

ABSTRACT: Because of the inertness of molecular nitrogen, its practicable activation under mild conditions is a fundamental challenge. Ta₃ ^- is an exceptionally small cluster that reacts with N₂ at room temperature, leading finally to Ta₃N₂ ^-; Ta₃N₂ ^- also could react with N₂ at room temperature, leading finally to Ta₃N₄ ^-, a product of interest in its own right because of its potential as a nitrogen fixation medium. The mechanisms of the Ta₃ ^-- and Ta₃N₂ ^--mediated activation of the N≡N triple bond have been investigated. Our extensive computations elucidate mechanisms for the ready reactions, leading to stepwise cleavage of the N≡N bond. Initial isomeric N₂/Ta₃ ^- complexes, N≡N elongation, undergo a N≡N split over generally low barriers in a highly exothermic process. The nitrogen-atom or molecular exchange reactions found in the Ta₃N₂ ^-/N₂ system may be of paramount importance in both applied and fundamental studies.

SUBMITTER: Sun X

PROVIDER: S-EPMC9260930 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Reaction of Ta3 - Clusters with Molecular Nitrogen: A Mechanism Investigation.

Sun Xiaoli X Huang Xuri X

ACS omega 20220621 26

Because of the inertness of molecular nitrogen, its practicable activation under mild conditions is a fundamental challenge. Ta3 - is an exceptionally small cluster that reacts with N2 at room temperature, leading finally to Ta3N2 -; Ta3N2 - also could react with N2 at room temperature, leading finally to Ta3N4 -, a product of interest in its own right be ...[more]

PMID: 35811866

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Project description:The reaction of excited nitrogen atoms N(2D) with CH3CCH (methylacetylene) was investigated under single-collision conditions by the crossed molecular beams (CMB) scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy (Ec) of 31.0 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction micromechanism. Theoretically, the reaction is found to proceed via a barrierless addition of N(2D) to the carbon-carbon triple bond of CH3CCH and an insertion of N(2D) into the CH bond of the methyl group, followed by the formation of cyclic and linear intermediates that can undergo H, CH3, and C2H elimination or isomerize to other intermediates before unimolecularly decaying to a variety of products. Kinetic calculations for addition and insertion mechanisms and statistical (Rice-Ramsperger-Kassel-Marcus) computations of product branching fractions (BFs) on the theoretical PES were performed at different values of total energy, including the one corresponding to the temperature (175 K) of Titan's stratosphere and that of the CMB experiment. Up to 14 competing product channels were statistically predicted, with the main ones, at Ec = 31.0 kJ/mol, being the formation of CH2NH (methanimine) + C2H (ethylidyne) (BF = 0.41), c-C(N)CH + CH3 (BF = 0.32), CH2CHCN (acrylonitrile) + H (BF = 0.12), and c-CH2C(N)CH + H (BF = 0.04). Of the 14 possible channels, seven correspond to H displacement channels of different exothermicity, for a total H channel BF of ∼0.25 at Ec = 31.0 kJ/mol. Experimentally, dynamical information could only be obtained about the overall H channels. In particular, the experiment corroborates the formation of acrylonitrile + H, which is the most exothermic of all 14 reaction channels and is theoretically calculated to be the dominant H-forming channel (BF = 0.12). The products containing a novel C-N bond could be potential precursors to form other nitriles (C2N2, C3N) or more complex organic species containing N atoms in planetary atmospheres, such as those of Titan and Pluto. Overall, the results are expected to have a potentially significant impact on the understanding of the gas-phase chemistry of Titan's atmosphere and the modeling of that atmosphere.

Dataset Information

Reaction of Ta₃ ^- Clusters with Molecular Nitrogen: A Mechanism Investigation.

Publications

Reaction of Ta<sub>3</sub> <sup>-</sup> Clusters with Molecular Nitrogen: A Mechanism Investigation.

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