Infrared diode laser study of the kinetics of the NCCO+O2 reaction

Feng, Wenhui; Hershberger, John F.

doi:10.1016/j.cplett.2010.02.029

Cited by 5 publications

(25 citation statements)

References 25 publications

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“…6 In our previous study of the NCCO + O 2 reaction, we estimated a somewhat lower value of Φ 2a = 62%, 15 with a significant yield of CO and CN product (eq 2c) as well.…”

Section: Methodsmentioning

confidence: 98%

“…1À17 We have recently detected the NCCO radical at 1887À1889 cm À1 in the gas phase using high resolution diode IR spectroscopy. 15 Allen et al used FTIR spectroscopy on matrix-isolated NCCO, finding a strong v 2 transition at 1890 cm À1 . 16 Recently, we have used this spectroscopic assignment to probe NCCO in several kinetics experiments.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of the NCCO + NO₂ Reaction

Feng

Hershberger

2011

J. Phys. Chem. A

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The kinetics of the NCCO + NO(2) reaction was studied by transient infrared laser absorption spectroscopy. The total rate constant of the reaction was measured to be k = (2.1 ± 0.1) × 10(-11) cm(3) molecule(-1) s(-1) at 298 K. Detection of products and consideration of possible secondary chemistry shows that CO(2) + NO + CN is the primary product channel. The rate constants of the NCCO + CH(4) and NCCO + C(2)H(4) reactions were also measured, obtaining upper limits of k (NCCO + CH(4)) ≤ 7.0 × 10(-14) cm(3) molecule(-1) s(-1) and k (NCCO + C(2)H(4)) ≤ 5.0 × 10(-15) cm(3) molecule(-1) s(-1). Ab initio calculations on the singlet and triplet potential energy surfaces at B3LYP/6-311++G**//CCSD(T)/6-311++G** levels of theory show that the most favorable reaction pathway occurs on the singlet surface, leading to CO(2) + NO + CN products, in agreement with experiment.

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“…6 In our previous study of the NCCO + O 2 reaction, we estimated a somewhat lower value of Φ 2a = 62%, 15 with a significant yield of CO and CN product (eq 2c) as well.…”

Section: Methodsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Kinetics of the NCCO + NO₂ Reaction

Feng

Hershberger

2011

J. Phys. Chem. A

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“…1800-2350 cm −1 . The low energy side of this band may contain contributions from the ν 2 CO stretch of NCCO (1889 cm −1 fundamental 21,52 ). Nevertheless, due to the spectral congestion of this band, any contribution from NCCO is completely unresolvable.…”

Section: Results and Analysismentioning

confidence: 99%

“…Later, in a time-resolved infrared diode laser (IDL) study aimed at monitoring the reaction kinetics of the cyanooxymethyl (NCCO) radical, Feng and Hershberger described a third channel involving unimolecular dissociation of internally excited NCCO ‡ produced in reaction (1) 21 :…”

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confidence: 99%

Predissociation of methyl cyanoformate: The HCN and HNC channels

Wilhelm,

Martínez-Núñez,

González-Vázquez

et al. 2016

Preprint

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We present a combined experimental and theoretical investigation of the 193 nm photolysis of the cyano-ester, methyl cyanoformate (MCF). Specifically, nanosecond time-resolved infrared emission spectroscopy was used to monitor the ro-vibrationally excited photoproducts generated in the photolysis reaction. The signal-to-noise of all time-resolved spectra were enhanced using the recently developed algorithm, spectral reconstruction analysis, which allowed observation of previously obscured minor resonances, and revealed new dissociation channels producing HCN and HNC. Spectral fit analysis of the nascent HCN and electronically excited CN(A 2 Π 1 ) resonances yield a lower bound estimate for the HCN quantum yield of ca. 0.42±0.24%. Multi-configuration self-consistent field calculations were used to interrogate the ground and four lowest energy singlet excited states of MCF. At 193 nm, dissociation is predicted to occur predominantly on the repulsive S 2 state. Nevertheless, minor pathways leading to the production of highly excited ground state MCF are available via cascading internal conversion from nascent S 2 population. An automated transition-state search algorithm was employed to identify the corresponding ground state dissociation channels, and Rice-Ramsperger-Kassel-Marcus and Kinetic Monte Carlo kinetic simulations were used to calculate the associated branching ratios. The proposed mechanism was validated by direct comparison of the experimentally measured and quasi-classical trajectory deduced nascent internal energy distribution of HCN, which were found to be in near perfect agreement. The propensity for cyano containing hydrocarbons to act as photolytic sources for ro-vibrationally excited HCN and HNC, as well as their significance to astrophysical environments, are discussed.

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“…6 In our previous study of the NCCO + O 2 reaction, we estimated a somewhat lower value of Φ 2a ) 62%, 15 with a smaller but significant yield of product channel 2c as well.…”

Section: Methodsmentioning

confidence: 97%

Kinetics and Mechanism of the NCCO + NO Reaction

Feng

Hershberger

2010

J. Phys. Chem. A

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The kinetics of the NCCO + NO reaction was studied by diode infrared laser spectroscopy. The results show that the total rate coefficient of the reaction is highly pressure dependent, with k(1) (298 K) = (3.2 +/- 0.5 to 27.1 +/- 2.0) x 10(-13) cm(3) molecule(-1) s(-1) over the total pressure range 3-25 Torr. Only very small yields of CO(2) and CO products were detected, with upper limits on branching ratios estimated at Phi (CO(2) + NCN) < or = 0.01, Phi (2NCO) < or = 0.01, and Phi(CO + NCNO) < or = 0.06. The reaction mechanism was investigated by calculating the potential energy surface (PES) using ab initio methods at the DFT-B3LYP/6-311++G**//CCSD(T)/6-311++G** level. The PES shows that pathways leading to bimolecular/trimolecular product channels involve high barriers. Both experiment and theory therefore indicate that the major pathway is formation and collisional stabilization of an NCC(NO)O adduct.

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Infrared diode laser study of the kinetics of the NCCO+O2 reaction

Cited by 5 publications

References 25 publications

Kinetics of the NCCO + NO₂ Reaction

Kinetics of the NCCO + NO₂ Reaction

Predissociation of methyl cyanoformate: The HCN and HNC channels

Kinetics and Mechanism of the NCCO + NO Reaction

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Infrared diode laser study of the kinetics of the NCCO+O2 reaction

Cited by 5 publications

References 25 publications

Kinetics of the NCCO + NO2 Reaction

Kinetics of the NCCO + NO2 Reaction

Predissociation of methyl cyanoformate: The HCN and HNC channels

Kinetics and Mechanism of the NCCO + NO Reaction

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Product

Resources

About

Kinetics of the NCCO + NO₂ Reaction

Kinetics of the NCCO + NO₂ Reaction