Measurement of the rate constant for the association reaction CH + N<sub>2</sub> at 53 K and its relevance to Triton's atmosphere

Picard, Sébastien D. Le; Canosa, André

doi:10.1029/98gl50118

Cited by 8 publications

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References 16 publications

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“…At low temperatures, stabilization to HCNN dominates the kinetics observed in a number of experimental studies. − This stabilization is irrelevant to the question of prompt NO, and so we do not consider this aspect further. At temperatures of 1000 K and higher, stabilization in this HCNN well becomes insignificant.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of CH + N₂ Revisited with Multireference Methods

2008

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The potential energy surface for the CH + N2 reaction was reexamined with multireference ab initio electronic structure methods employing basis sets up to aug-cc-pvqz. Comparisons with related CCSD(T) calculations were also made. The multireference ab initio calculations indicate significant shortcomings in single reference based methods for two key rate-limiting transition states. Transition state theory calculations incorporating the revised best estimates for the transition state properties provide order of magnitude changes in the predicted rate coefficient in the temperature range of importance to the mechanism for prompt NO formation. At higher temperatures, two distinct pathways make a significant contribution to the kinetics. A key part of the transition state analysis involves a variable reaction coordinate transition state theory treatment for the formation of H + NCN from HNCN. The present predictions for the rate coefficients resolve the discrepancy between prior theory and very recent experimental measurements.

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Section: Methodsmentioning

confidence: 99%

Kinetics of CH + N₂ Revisited with Multireference Methods

2008

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“…The reaction of CH with N 2 is of considerable importance at low temperatures in the chemistry of planetary atmospheres and at high temperatures in combustion chemistry. The low-temperature reaction proceeds by the barrierless formation of a datively bonded addition complex, HCNN. − At the high temperatures of combustion environments, the reaction is believed to be dominated by pathways that lead to the production of the “prompt” NO seen in flames . Initially, a spin-forbidden pathway in which HCN (X 1 Σ + ) + N( 4 S) are produced had been postulated, − whereas more recently, Lin and co-workers proposed that the dominant route in combustion produces H + NCN ( 3 Σ - g ) in a spin-allowed process that passes through an HNCN intermediate.…”

Section: Introductionmentioning

confidence: 99%

HNNC Radical and Its Role in the CH + N₂ Reaction

et al. 2007

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A previously unreported channel in the spin-allowed reaction path for the CH+N2 reaction that involves the HNNC radical is presented. The structures and energetics of the HNNC radical and its isomers HCNN and HNCN and the relevant intermediates and transition states that are involved in the proposed mechanism are obtained at the coupled cluster singles and doubles level of theory with noniterative triples correction (CCSD(T)) using a converging series of basis sets aug-cc-pVDZ, aug-cc-pVTZ, and aug-cc-pVQZ. The aug-cc-pVQZ basis is used for all the final single point energy calculations using the CCSD(T)/aug-cc-pVTZ optimized geometries. We find the HNNC radical to have a heat of formation of DeltafH0 (HNNC)=116.5 kcal mol(-1). An assessment of the quality of computed data of the radical species HNCN and HCNN is presented by comparison with the available experimental data. We find that HNNC can convert to HNCN, the highest barrier in this path being 14.5 kcal mol(-1) above the energy of the CH+N2 reactants. Thus, HNNC can play a role in the high-temperature spin-allowed mechanism for the reaction of CH+N2 proposed by Moskaleva, Xia, and Lin (Chem. Phys. Lett. 2000, 331, 269).

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Chemie mit Überschall: 30 Jahre astrochemische Forschung und künftige Herausforderungen

et al. 2017

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Das interstellare Medium ist für uns von großem Interesse. Hier werden Sterne und Planeten geboren und wahrscheinlich sind von hier molekulare Vorstufen des Lebens zur Erde gelangt. Um die chemischen Wege zur Bildung von Sternen, Planeten und biologischen Molekülen zu verstehen, sollten astronomische Beobachtungen, astrochemische Modellierung und Laborastrochemie Hand in Hand arbeiten. Hier stellen wir Laborexperimente vor, die sich der Untersuchung der Reaktionsdynamik von astrochemisch interessanten Spezies bei Temperaturen des interstellaren Mediums widmen und die unter Verwendung von CRESU, einer der populärsten Techniken in diesem Bereich, durchgeführt wurden. Außerdem diskutieren wir neue technische Entwicklungen und wissenschaftliche Ideen zur CRESU, die unser Verständnis der astrochemischen Geschichte und Zukunft unseres Universums einen Schritt weiter bringen könnten.

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Measurement of the rate constant for the association reaction CH + N₂ at 53 K and its relevance to Triton's atmosphere

Cited by 8 publications

References 16 publications

Kinetics of CH + N₂ Revisited with Multireference Methods

Kinetics of CH + N₂ Revisited with Multireference Methods

HNNC Radical and Its Role in the CH + N₂ Reaction

Chemie mit Überschall: 30 Jahre astrochemische Forschung und künftige Herausforderungen

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Measurement of the rate constant for the association reaction CH + N2 at 53 K and its relevance to Triton's atmosphere

Cited by 8 publications

References 16 publications

Kinetics of CH + N2 Revisited with Multireference Methods

Kinetics of CH + N2 Revisited with Multireference Methods

HNNC Radical and Its Role in the CH + N2 Reaction

Chemie mit Überschall: 30 Jahre astrochemische Forschung und künftige Herausforderungen

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Product

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Measurement of the rate constant for the association reaction CH + N₂ at 53 K and its relevance to Triton's atmosphere

Kinetics of CH + N₂ Revisited with Multireference Methods

Kinetics of CH + N₂ Revisited with Multireference Methods

HNNC Radical and Its Role in the CH + N₂ Reaction