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Atmospheric Oxidation of Furan and Methyl-Substituted Furans Initiated by Hydroxyl Radicals
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-28 00:00:00 , DOI: 10.1021/acs.jpca.7b09741 Yi Yuan 1 , Xiaocan Zhao 1 , Sainan Wang 1 , Liming Wang 1, 2
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-28 00:00:00 , DOI: 10.1021/acs.jpca.7b09741 Yi Yuan 1 , Xiaocan Zhao 1 , Sainan Wang 1 , Liming Wang 1, 2
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The atmospheric oxidation mechanism of furan and methylfurans (MFs) initiated by OH radicals is studied using high-level quantum chemistry and kinetic calculations. The reaction starts mainly with OH addition to the C2/C5-position, forming highly chemically activated adduct radical R2*/R5*, which would either be stabilized by collision or promptly isomerize to R2B*/R5B* by breaking the C2-O/C5-O bond and then isomerize to other conformers of R2B/R5B by internal rotations. Under the atmospheric conditions, the ring-retaining radical R2/R5 would recombine with O2 and be converted to a 5-hydroxy-2-furanone compound and a compound containing epoxide, ester, and carbonyl functional groups, while the ring-opening radicals R2B/R5B would react with O2 and form unsaturated 1,4-dicarbonyl compounds. RRKM-ME calculations on the fate of R2*/R5* from the addition of OH and furans predict that the fractions of R2B/R5B formation, i.e., the molar yields of the corresponding dicarbonyl compounds, are 0.73, 0.43, 0.26, 0.07, and 0.28 for furan, 2-MF, 3-MF, 2,3-DMF, and 2,5-DMF, respectively, at 298 K and 760 Torr when using the RHF-UCCSD(T)-F12a/cc-pVDZ-F12 reaction energies and barrier heights. The predicted yields for dicarbonyl compounds agree reasonably with recent experimental measurements. Calculations here also suggest high yields of ring-retaining 5-hydroxy-2-furanone compounds, which might deserve further study.
中文翻译：
羟基自由基引发的呋喃和甲基取代的呋喃的大气氧化
使用高级量子化学和动力学计算研究了由OH自由基引发的呋喃和甲基呋喃（MFs）在大气中的氧化机理。反应主要从向C2 / C5位置加OH开始，形成高度化学活化的加成基R2 * / R5 *，该基团可通过碰撞稳定，或通过破坏C2-O /而迅速异构化为R2B * / R5B *。 C5-O键，然后通过内部旋转异构化为R2B / R5B的其他构象异构体。在大气条件下，R2 / R5的开环基团将与O 2结合并转化为5-羟基-2-呋喃酮化合物和含有环氧化物，酯和羰基官能团的化合物，而开环基团R2B / R5B会与O 2反应并形成不饱和的1，4-二羰基化合物。通过OH和呋喃的添加对R2 * / R5 *的命运进行的RRKM-ME计算预测，R2B / R5B形成的分数（即相应的二羰基化合物的摩尔产率）为0.73、0.43、0.26、0.07，使用RHF-UCCSD（T）-F12a / cc-pVDZ-时，呋喃，2-MF，3-MF，2,3-DMF和2,5-DMF分别为298 K和760 Torr时为0.28。 F12反应能和势垒高度。二羰基化合物的预测收率与最近的实验测量结果相当吻合。此处的计算还表明保持环的5-羟基-2-呋喃酮化合物的收率高，这可能值得进一步研究。
更新日期：2017-11-28
中文翻译：
羟基自由基引发的呋喃和甲基取代的呋喃的大气氧化
使用高级量子化学和动力学计算研究了由OH自由基引发的呋喃和甲基呋喃（MFs）在大气中的氧化机理。反应主要从向C2 / C5位置加OH开始，形成高度化学活化的加成基R2 * / R5 *，该基团可通过碰撞稳定，或通过破坏C2-O /而迅速异构化为R2B * / R5B *。 C5-O键，然后通过内部旋转异构化为R2B / R5B的其他构象异构体。在大气条件下，R2 / R5的开环基团将与O 2结合并转化为5-羟基-2-呋喃酮化合物和含有环氧化物，酯和羰基官能团的化合物，而开环基团R2B / R5B会与O 2反应并形成不饱和的1，4-二羰基化合物。通过OH和呋喃的添加对R2 * / R5 *的命运进行的RRKM-ME计算预测，R2B / R5B形成的分数（即相应的二羰基化合物的摩尔产率）为0.73、0.43、0.26、0.07，使用RHF-UCCSD（T）-F12a / cc-pVDZ-时，呋喃，2-MF，3-MF，2,3-DMF和2,5-DMF分别为298 K和760 Torr时为0.28。 F12反应能和势垒高度。二羰基化合物的预测收率与最近的实验测量结果相当吻合。此处的计算还表明保持环的5-羟基-2-呋喃酮化合物的收率高，这可能值得进一步研究。
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