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首页> 外文期刊>Environmental Science & Technology >Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals
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Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals

机译：通过量子化学计算开发有机化合物与臭氧在水溶液中反应性的预测模型：离域和局域分子轨道的作用

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摘要

Second-order rate constants (k_(O_3)) for the reaction of ozone with micropollutants are essential parameters for the assessment of micropollutant elimination efficiency during ozonation in water and wastewater treatment. Prediction models for k_(O3) were developed for aromatic compounds, olefins, and amines by quantum chemical molecular orbital calculations employing ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods. The k_(O_3) values for aromatic compounds correlated well with the energy of a delocalized molecular orbital first appearing on an aromatic ring (i.e., the highest occupied molecular orbital (HOMO) or HOMO-n (n＞ 0) when the HOMO is not located on the aromatic ring); the number of compounds tested (N) was 112, and the correlation coefficient (R~2) values were 0.82-1.00. The k_(O_3) values for olefins and amines correlated well with the energy of a localized molecular orbital (i.e., the natural bond orbital (NBO)) energy of the carbon-carbon n bond of olefins (N = 45, R~2 values of 0.82-0.85) and the NBO energy of the nitrogen lone-pair electrons of amines (N = 59, R~2 values of 0.81-0.83), respectively. Considering the performance of the k_(O_3) prediction model and the computational costs, the HF/6-31G method is recommended for all aromatic groups and olefins investigated herein, whereas the HF/MIDI!, HF/6-31G~*, or HF/6-311++G~(**) methods are recommended for amines. Based on their mean absolute errors, the above models could predict k_(O_3) within a factor of 4, on average, relative to the experimentally determined values. Overall, good correlations were also observed (R2 values of 0.77-0.96) between k_(O_3) predictions by quantum molecular orbital descriptors in this study and by the Hammett (σ) and Taft (σ~*) constants from previously developed quantitative structure-activity relationship (QSAR) models. Hence, the quantum molecular orbital descriptors are an alternative to σ and σ~*-values in QSAR applications and can also be utilized to estimate unknown σ or σ~*-values.
机译：臭氧与微污染物的反应的二级速率常数（k_（O_3））是评估水和废水处理中臭氧氧化过程中微污染物消除效率的必要参数。通过从头算Hartree-Fock（HF）和密度泛函理论（B3LYP）方法的量子化学分子轨道计算，开发了k_（O3）的预测模型，用于芳香族化合物，烯烃和胺。芳香族化合物的k_（O_3）值与首先出现在芳香环上的离域分子轨道的能量（即最高占据分子轨道（HOMO）或HOMO-n（n＞ 0））具有良好的相关性位于芳环上）；被测化合物（N）为112，相关系数（R〜2）值为0.82-1.00。烯烃和胺的k_（O_3）值与烯烃的碳-碳n键的局部分子轨道的能量（即自然键轨道（NBO））的能量很好相关（N = 45，R〜2值分别为0.82-0.85）和胺的氮孤对电子的NBO能量（N = 59，R〜2值为0.81-0.83）。考虑到k_（O_3）预测模型的性能和计算成本，建议对本文研究的所有芳族基团和烯烃使用HF / 6-31G方法，而HF / MIDI！，HF / 6-31G〜*或对于胺类，推荐使用HF / 6-311 ++ G〜（**）方法。基于它们的平均绝对误差，相对于实验确定的值，上述模型可以将k_（O_3）平均预测为4。总体而言，在这项研究中，量子分子轨道描述子与哈密特（σ）和塔夫脱（σ〜*）常数之间的k_（O_3）预测与先前开发的定量结构的常数之间也观察到了良好的相关性（R2值为0.77-0.96）。活动关系（QSAR）模型。因此，在QSAR应用中，量子分子轨道描述符是σ和σ〜*值的替代方法，并且还可用于估算未知的σ或σ〜*值。

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  • 来源
    《Environmental Science & Technology》 |2015年第16期|9925-9935|共11页
  • 作者

    Minju Lee; Saskia G. Zimmermann-Steffens; J. Samuel Arey; Kathrin Fenner; Urs von Gunten;

  • 作者单位

    School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique Federate de Lausanne (EPFL), CH-101S, Lausanne, Switzerland;

    School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique Federate de Lausanne (EPFL), CH-101S, Lausanne, Switzerland ,Federal Office for the Environment (FOEN), Bern 3003, Switzerland;

    School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique Federate de Lausanne (EPFL), CH-101S, Lausanne, Switzerland ,Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf, Switzerland;

    Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf, Switzerland ,Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich, CH-8092 Zurich, Switzerland;

    School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique Federate de Lausanne (EPFL), CH-101S, Lausanne, Switzerland ,Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf, Switzerland ,Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich, CH-8092 Zurich, Switzerland;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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