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Ab Initio Chemical Kinetics for the OH HNCN Reaction.

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Title: Ab Initio Chemical Kinetics for the OH HNCN Reaction.
Authors: Shucheng Xu1, M. C. Lin1
Source: Journal of Physical Chemistry A. Jul2007, Vol. 111 Issue 29, p6730-6740. 11p.
Subjects: Physical & theoretical chemistry, Science, Chemistry, Physical sciences
Abstract: The kinetics and mechanism of the reaction of the cyanomidyl radical (HNCN) with the hydroxyl radical (OH) have been investigated by ab initio calculations with rate constants prediction. The single and triplet potential energy surfaces of this reaction have been calculated by single-point calculations at the CCSD(T)/6-311G(3df,2p) level based on geometries optimized at the B3LYP/6-311G(3df,2p) and CCSD/6-311 G(d,p) levels. The rate constants for various product channels in the temperature range of 300−3000 K are predicted by variational transition-state and Rice−Ramsperger−Kassel−Marcus (RRKM) theories. The predicted total rate constants can be represented by the expressions ktotal2.66 × 102× T-4.50exp(−239/T) in which T300−1000 K and 1.38 × 10-20× T2.78exp(1578/T) cm3molecule-1s-1where T1000−3000 K. The branching ratios of primary channels are predicted:  k1for forming singlet HON(H)CN accounts for 0.32−0.28, and k4for forming singlet HONCNH accounts for 0.68−0.17 in the temperature range of 300−800 K. k2k7for producing H2O NCN accounts for 0.55−0.99 in the high-temperature range of 800−3000 K. The branching ratios of k3for producing HCN HNO, k6for producing H2N NCO, k8for forming 3HN(OH)CN, k9for producing CNOH 3NH, and k5k10for producing NH2NCO are negligible. The rate constants for key individual product channels are provided in a table for different temperature and pressure conditions. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Ab Initio Chemical Kinetics for the OH HNCN Reaction.
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  Data: <searchLink fieldCode="AR" term="%22Shucheng+Xu%22">Shucheng Xu</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22M%2E+C%2E+Lin%22">M. C. Lin</searchLink><relatesTo>1</relatesTo>
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  Data: The kinetics and mechanism of the reaction of the cyanomidyl radical (HNCN) with the hydroxyl radical (OH) have been investigated by ab initio calculations with rate constants prediction. The single and triplet potential energy surfaces of this reaction have been calculated by single-point calculations at the CCSD(T)/6-311G(3df,2p) level based on geometries optimized at the B3LYP/6-311G(3df,2p) and CCSD/6-311 G(d,p) levels. The rate constants for various product channels in the temperature range of 300−3000 K are predicted by variational transition-state and Rice−Ramsperger−Kassel−Marcus (RRKM) theories. The predicted total rate constants can be represented by the expressions ktotal2.66 × 102× T-4.50exp(−239/T) in which T300−1000 K and 1.38 × 10-20× T2.78exp(1578/T) cm3molecule-1s-1where T1000−3000 K. The branching ratios of primary channels are predicted:  k1for forming singlet HON(H)CN accounts for 0.32−0.28, and k4for forming singlet HONCNH accounts for 0.68−0.17 in the temperature range of 300−800 K. k2k7for producing H2O NCN accounts for 0.55−0.99 in the high-temperature range of 800−3000 K. The branching ratios of k3for producing HCN HNO, k6for producing H2N NCO, k8for forming 3HN(OH)CN, k9for producing CNOH 3NH, and k5k10for producing NH2NCO are negligible. The rate constants for key individual product channels are provided in a table for different temperature and pressure conditions. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/jp069038+
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        Text: English
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      – TitleFull: Ab Initio Chemical Kinetics for the OH HNCN Reaction.
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