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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >2 1Δg)]]>
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2 1Δg)]]>

机译：<！[CDATA [苯胺与单向氧气的反应（O 2 1 δ g ）]>

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Dissolved organic matter (DOM) acts as an effective photochemical sensitizer that produces the singlet delta state of molecular oxygen (O2 1Δg), a powerful oxidizer that removes aniline from aqueous solutions. However, the exact mode of this reaction, the p- to o-iminobenzoquinone ratio, and the selectivity of one over the other remain largely speculative. This contribution resolves these uncertainties. We report, for the first time, a comprehensive mechanistic and kinetic account of the oxidation of aniline with the singlet delta oxygen using B3LYP and M06 functionals in both gas and aqueous phases. Reaction mechanisms have been mapped out at E, H, and G scales. The 1,4-cycloaddition of O2 1Δg to aniline forms a 1,4-peroxide intermediate (M1), which isomerizes via a closed-shell mechanism to generate a p-iminobenzoquinone molecule. On the other hand, the O2 1Δg ene-type reaction forms an o-iminobenzoquinone product when the hydroperoxyl bond breaks, splitting hydroxyl from the 1,2-hydroperoxide (M3) moiety. The gas-phase model predicts the formation of both p- and o-iminobenzoquinones. In the latter model, the M1 adduct displays the selectivity of up to 96%. A water-solvation model predicts that M1 decomposes further, forming only p-iminobenzoquinone with a rate constant of k = 1.85 × 109 (L/(mol s)) at T = 313 K. These results corroborate the recent experimental findings of product concentration profile in which p-iminobenzoquinonine represents the only detected product.]]>
机译：<！[cdata [ src ='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jpcafh/2017/jpcafh.2017.121.issue-17/acs.jpca.7b00765/ 20170428 /图像/培养基/ JP-2017-00765J_0001.gif“>溶解的有机物（DOM）作为一种有效的光化学敏化剂，其产生分子氧的单次δ（O 2 1 δ<亚> g ），一种从水溶液中除去苯胺的强氧化剂。然而，该反应的确切模式， P - / I>至 -Im oImobenzoquinone比率，并且彼此相对的选择性仍然在很大程度上是推测性的。这一贡献解决了这些不确定性。我们首次报告了使用B3LYP和M06在气相和水相中的酸胆碱的氧化氧化综合机械和动力学陈述。在 e ， h℃和 g / i>尺度下映射了反应机制。 O 2 1 δ g / sub>对苯胺的1,4-环绕编辑为1,4-过氧化物中间体（m1），其异构化一种封闭的壳体机制，用于产生 P -iminobenzoquinone分子。另一方面，O 2 1 δ g / sum>烯型反应在其中形成-Iminobenzoquinone产品氢过氧基键断裂，分离来自1,2-氢过氧化物（M3）部分的羟基。气相模型预测了 p - 和 o - 咪唑醌的形成。在后一种型号中，M1加合物显示最高96％的选择性。水溶化模型预测M1进一步分解，仅形成 P -Iminobzoquinone，其速率常数为 k = 1.85×10 9 （l /（mol s））在 t = 313k。这些结果证实了最近的产品浓度谱的实验结果，其中 p -iminobenzoquinonine代表唯一检测到的产品。]]]] >

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