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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactions of Chemically Activated Formic Acid Formed via H(C) over dotO plus (O) over dotH
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Reactions of Chemically Activated Formic Acid Formed via H(C) over dotO plus (O) over dotH

机译:通过dotO上的H(C)和dotH上的(O)形成的化学活化甲酸的反应

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摘要

The chemistry of formyl radicals plays an important role in the kinetic modeling of oxygenated hydrocarbons. Here, the fate of rovibrationally excited formic acid produced via H(C) over dotO + (O) over dotH is evaluated in a RKKM/Master Equation study. For that purpose, the H(C) over dotO + (O) over dotH potential energy surface is studied theoretically using high-level quantum mechanics. Direct reaction from H(C) over dotO + (O) over dotH to the bimolecular products is found to dominate for most relevant conditions due to formic acid well-skipping. The kinetics of these well skipping reactions can only be evaluated when including the unimolecular intermediate, formic acid. Further, hydrogen abstraction from rovibrationally excited formic acid is found to be important at low-temperature conditions and for high radical concentrations.
机译:甲酰基的化学在氧化烃的动力学建模中起重要作用。在此,在RKKM / Master方程研究中评估了通过H(C)在dotO +(O)之上在dotH上通过H(C)产生的预激激发甲酸的去向。为此,理论上使用高级量子力学对dotO上的H(C)+ dotH上的O(O)进行了研究。由于甲酸井漏现象,在大多数相关条件下,从H(C)于dotO +(O)于dotH到双分子产物的直接反应占主导地位。仅当包括单分子中间体甲酸时,才能评估这些跳井反应的动力学。此外,发现在低温条件下和高自由基浓度下,从激子激发的甲酸中提取氢很重要。

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