Theoretical studies of nitroamino radical reactions: Rate constants for the unimolecular decomposition of HNNO
                        2
                         and related bimolecular processes

D. Chakraborty; C. C. Hsu; Ming-Chang Lin

doi:10.1063/1.477560

Theoretical studies of nitroamino radical reactions: Rate constants for the unimolecular decomposition of HNNO ₂ and related bimolecular processes

D. Chakraborty^*, C. C. Hsu, Ming-Chang Lin

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

The unimolecular decomposition of HNNO ₂ and the related bimolecular reaction of NH with NO ₂ have been studied by high-level ab initio molecular orbital and statistical theory calculations. The potential energy surface for the bimolecular association leading to the formation of HNNO ₂ and HNONO, the formation of exothermic products N ₂ O and OH via the HNNO ₂ intermediate, and of HNO and NO via the HNONO intermediate have been computed with a modified GAUSSIAN 2 (G2M) method. The rate constants for these two bimolecular reaction channels have been calculated by means of the canonical variational Rice-Ramsperger-Kassel-Marcus (RRKM) approach over a broad temperature range. The predicted values at room temperature correlate reasonably well with the experimental overall rate and also with the experimental product branching probability for the formation of N ₂ O vs HNO via the nitro and nitrite intermediates. The effect of multiple reflections within the potential well of the HN-ONO complex was found to be quite significant. It reduces the rate constant for the formation of the HNO+NO products by as much as 350%.

Original language	English
Pages (from-to)	8887-8896
Number of pages	10
Journal	Journal of Chemical Physics
Volume	109
Issue number	20
DOIs	https://doi.org/10.1063/1.477560
State	Published - 1 Jan 1998

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title = "Theoretical studies of nitroamino radical reactions: Rate constants for the unimolecular decomposition of HNNO 2 and related bimolecular processes",

abstract = " The unimolecular decomposition of HNNO 2 and the related bimolecular reaction of NH with NO 2 have been studied by high-level ab initio molecular orbital and statistical theory calculations. The potential energy surface for the bimolecular association leading to the formation of HNNO 2 and HNONO, the formation of exothermic products N 2 O and OH via the HNNO 2 intermediate, and of HNO and NO via the HNONO intermediate have been computed with a modified GAUSSIAN 2 (G2M) method. The rate constants for these two bimolecular reaction channels have been calculated by means of the canonical variational Rice-Ramsperger-Kassel-Marcus (RRKM) approach over a broad temperature range. The predicted values at room temperature correlate reasonably well with the experimental overall rate and also with the experimental product branching probability for the formation of N 2 O vs HNO via the nitro and nitrite intermediates. The effect of multiple reflections within the potential well of the HN-ONO complex was found to be quite significant. It reduces the rate constant for the formation of the HNO+NO products by as much as 350%.",

author = "D. Chakraborty and Hsu, {C. C.} and Ming-Chang Lin",

year = "1998",

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doi = "10.1063/1.477560",

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volume = "109",

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journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

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Theoretical studies of nitroamino radical reactions: Rate constants for the unimolecular decomposition of HNNO ₂ and related bimolecular processes. / Chakraborty, D.; Hsu, C. C.; Lin, Ming-Chang.
In: Journal of Chemical Physics, Vol. 109, No. 20, 01.01.1998, p. 8887-8896.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Theoretical studies of nitroamino radical reactions

T2 - Rate constants for the unimolecular decomposition of HNNO 2 and related bimolecular processes

AU - Chakraborty, D.

AU - Hsu, C. C.

AU - Lin, Ming-Chang

PY - 1998/1/1

Y1 - 1998/1/1

N2 - The unimolecular decomposition of HNNO 2 and the related bimolecular reaction of NH with NO 2 have been studied by high-level ab initio molecular orbital and statistical theory calculations. The potential energy surface for the bimolecular association leading to the formation of HNNO 2 and HNONO, the formation of exothermic products N 2 O and OH via the HNNO 2 intermediate, and of HNO and NO via the HNONO intermediate have been computed with a modified GAUSSIAN 2 (G2M) method. The rate constants for these two bimolecular reaction channels have been calculated by means of the canonical variational Rice-Ramsperger-Kassel-Marcus (RRKM) approach over a broad temperature range. The predicted values at room temperature correlate reasonably well with the experimental overall rate and also with the experimental product branching probability for the formation of N 2 O vs HNO via the nitro and nitrite intermediates. The effect of multiple reflections within the potential well of the HN-ONO complex was found to be quite significant. It reduces the rate constant for the formation of the HNO+NO products by as much as 350%.

AB - The unimolecular decomposition of HNNO 2 and the related bimolecular reaction of NH with NO 2 have been studied by high-level ab initio molecular orbital and statistical theory calculations. The potential energy surface for the bimolecular association leading to the formation of HNNO 2 and HNONO, the formation of exothermic products N 2 O and OH via the HNNO 2 intermediate, and of HNO and NO via the HNONO intermediate have been computed with a modified GAUSSIAN 2 (G2M) method. The rate constants for these two bimolecular reaction channels have been calculated by means of the canonical variational Rice-Ramsperger-Kassel-Marcus (RRKM) approach over a broad temperature range. The predicted values at room temperature correlate reasonably well with the experimental overall rate and also with the experimental product branching probability for the formation of N 2 O vs HNO via the nitro and nitrite intermediates. The effect of multiple reflections within the potential well of the HN-ONO complex was found to be quite significant. It reduces the rate constant for the formation of the HNO+NO products by as much as 350%.

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Theoretical studies of nitroamino radical reactions: Rate constants for the unimolecular decomposition of HNNO ₂ and related bimolecular processes

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