Weakly Bound Free Radicals in Combustion: “Prompt” Dissociation of Formyl Radicals and Its Effect on Laminar Flame Speeds

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• 作者：Nicole J. Labbe ; Raghu Sivaramakrishnan ; C. Franklin Goldsmith ; Yuri Georgievskii ; James A. Miller ; Stephen J. Klippenstein
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：January 7, 2016
• 年：2016
• 卷：7
• 期：1
• 页码：85-89
• 全文大小：317K
• ISSN：1948-7185

文摘

Weakly bound free radicals have low-dissociation thresholds such that at high temperatures, time scales for dissociation and collisional relaxation become comparable, leading to significant dissociation during the vibrational–rotational relaxation process. Here we characterize this “prompt” dissociation of formyl (HCO), an important combustion radical, using direct dynamics calculations for OH + CH₂O and H + CH₂O (key HCO-forming reactions). For all other HCO-forming reactions, presumption of a thermal incipient HCO distribution was used to derive prompt dissociation fractions. Inclusion of these theoretically derived HCO prompt dissociation fractions into combustion kinetics models provides an additional source for H-atoms that feeds chain-branching reactions. Simulations using these updated combustion models are therefore shown to enhance flame propagation in 1,3,5-trioxane and acetylene. The present results suggest that HCO prompt dissociation should be included when simulating flames of hydrocarbons and oxygenated molecules and that prompt dissociations of other weakly bound radicals may also impact combustion simulations.