Abstract

Criegee intermediates, which are the result of ozonolysis of alkenes, play a key role in many chemical and physical processes in the Earth’s atmosphere. Their reactions with various atmospheric compounds are responsible for formation of hydroxyl radicals, atomic oxygen and hydrogen, sulfuric and nitric acids, and other chemically active radicals and molecules. In this work we have considered collisional-induced chemical reactions between three simple Criegee intermediate molecules: CH₂OO, CH₃CHOO, and (CH₃)₂COO with methane, which is a well-known active greenhouse gas. Methane concentration rapidly growths last decades that causes serious concern to the global scientific community. It was established that reactions between methane and Criegee Intermediates can follow through two main routes. One of them occurs over exchange of oxygen and hydrogen atoms upon collision and leads to the formation of methanol. Another one pass through the formation of an intermediate complex with a deep energy minimum, and produces OH radicals and a variety of other products, among which are acetone, acetaldehyde, formaldehyde, propaldehyde, methanol, water molecules, and others. In this work, the both kinds of the reactions have been studied, and the relative reaction rates of both pathways have been compared.

中文翻译：

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甲烷与 Criegee 中间体 CH2OO、CH3CHOO 和 (CH3)2COO 之间碰撞引发的化学反应：理论研究

 抽象的

Criegee 中间体是烯烃臭氧分解的结果，在地球大气中的许多化学和物理过程中发挥着关键作用。它们与各种大气化合物发生反应，形成羟基自由基、原子氧和氢、硫酸和硝酸以及其他化学活性自由基和分子。在这项工作中，我们考虑了三个简单 Criegee 中间分子之间碰撞引起的化学反应：CH ₂ OO、CH ₃ CHOO 和 (CH ₃ ) < b3> COO 与甲烷，这是一种众所周知的活性温室气体。几十年来，甲烷浓度迅速增长，引起了全球科学界的严重关注。已确定甲烷和 Criegee 中间体之间的反应可以通过两条主要路线进行。其中之一发生在碰撞时氧和氢原子的交换并导致甲醇的形成。另一种则通过形成深度能量最低的中间配合物，产生OH自由基和多种其他产物，其中有丙酮、乙醛、甲醛、丙醛、甲醇、水分子等。在这项工作中，对这两种反应进行了研究，并比较了两种途径的相对反应速率。