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Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2023-05-22 , DOI: 10.1039/d3cp01075a Ilya S Sosulin 1 , Ekaterina S Shiryaeva 1 , Daniil A Tyurin 1 , Vladimir I Feldman 1
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2023-05-22 , DOI: 10.1039/d3cp01075a Ilya S Sosulin 1 , Ekaterina S Shiryaeva 1 , Daniil A Tyurin 1 , Vladimir I Feldman 1
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The investigation of the reactions of oxygen atoms with fluoroform (CHF3) molecules and products of their degradation present significant interest for better understanding of the impact of chemically inert fluorinated compounds on atmospheric chemistry and may provide a deeper insight into mechanisms of chemical processes occurring under the action of hard UV and ionizing radiation. In the present study we applied a matrix isolation technique with FTIR spectroscopic detection combined with ab initio calculations to address this issue. It was found that the reactions of “hot” (translationally excited) O(1D) atoms produced by X-ray or UV radiation from appropriate precursors (N2O or H2O) resulted in the formation of carbonyl fluoride (COF2) and its complex with HF. The complex was detected and characterized for the first time. Singlet oxygen atoms also probably react with the products of radiation-induced degradation of fluoroform (CF3 and CF2). Additionally, the reaction of “hot” O(3P) atoms with fluoroform may occur to a certain extent yielding the CF3 radical. No evidence for the reactions of thermal O(3P) atoms with CHF3 or products of its degradation was found under the experimental conditions used. The implications of the results of this model study for understanding the evolution of fluoroform in the upper layers of the stratosphere and ionosphere are discussed.
中文翻译：
氧原子与氟仿及其辐解产物的反应：基质分离和从头算研究
研究氧原子与氟仿 (CHF 3 ) 分子及其降解产物的反应，对于更好地了解化学惰性氟化化合物对大气化学的影响具有重要意义，并可能更深入地了解在以下情况下发生的化学过程的机制强紫外线和电离辐射的作用。在本研究中，我们应用矩阵隔离技术与 FTIR 光谱检测结合从头计算来解决这个问题。据发现，由适当的前体（N 2 O 或 H 2O) 导致形成碳酰氟 (COF 2 ) 及其与 HF 的络合物。该复合物是首次被检测和表征。单线态氧原子也可能与辐射诱导的氟仿降解产物（CF 3和 CF 2）发生反应。此外，“热”O( 3 P) 原子与氟仿的反应可能发生到一定程度，产生 CF 3自由基。没有证据表明热 O( 3 P) 原子与 CHF 3发生反应或其降解产物是在所用的实验条件下发现的。讨论了该模型研究结果对了解平流层和电离层上层氟仿演变的意义。
更新日期：2023-05-22
中文翻译：
氧原子与氟仿及其辐解产物的反应：基质分离和从头算研究
研究氧原子与氟仿 (CHF 3 ) 分子及其降解产物的反应，对于更好地了解化学惰性氟化化合物对大气化学的影响具有重要意义，并可能更深入地了解在以下情况下发生的化学过程的机制强紫外线和电离辐射的作用。在本研究中，我们应用矩阵隔离技术与 FTIR 光谱检测结合从头计算来解决这个问题。据发现，由适当的前体（N 2 O 或 H 2O) 导致形成碳酰氟 (COF 2 ) 及其与 HF 的络合物。该复合物是首次被检测和表征。单线态氧原子也可能与辐射诱导的氟仿降解产物（CF 3和 CF 2）发生反应。此外，“热”O( 3 P) 原子与氟仿的反应可能发生到一定程度，产生 CF 3自由基。没有证据表明热 O( 3 P) 原子与 CHF 3发生反应或其降解产物是在所用的实验条件下发现的。讨论了该模型研究结果对了解平流层和电离层上层氟仿演变的意义。
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