多环芳烃光解活性的量子化学研究
QUANTUM CHEMISTRY STUDY ON PHOTOLYSIS ACTIVITY OF POLYCYCLIC AROMATIC HYDROCARBONS
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摘要: 应用量子化学从头算HF/6-311+G(d)和B3LYP/6-311+G(d)方法计算了16种PAHs的多种量子化学参数,选取六种参数为分子结构的描述符,采用最小二乘法对16种PAHs的光解半衰期进行逐步多元线性回归分析,得到两个PAHs光解半衰期的QSAR模型,模型具有较高的相关系数,可有效地用于预测PAHs的光解半衰期.结果表明,HF方法所得模型优于B3LYP方法所得的模型.所得模型与基于半经验PM3算法的QSAR模型相比较,HF从头算方法所建立的QSAR模型比半经验PM3算法的结果要好.在所考查的诸多参数中,分子最高占有轨道特征值EHOMO,对PAHs光解半衰期起着决定作用.最后,运用所得模型预测了3种PAHs的光解半衰期.Abstract: Based on some quantum chemical descriptors computed at the HF/6-311+G(d)and B3LYP/6-311+G(d) level with the ab initio method of quantum chemistry, by the use of least squares analysis of six descriptors, two quantitative structure-activity relationship (QSAR) models for photolysis half-lives of selected 13 polycyclic aromatic hydrocarbons (PAHs) were obtained through stepwise multivariate linear regression. The correlation coefficients of the obtained models are significant. The results showed the HFtheory is better than B3LYPtheory in developing a QSAR model for photolysis half-lives of PAHs. The comparison of the obtained models in this study with the QSAR model based on the descriptors computed from PM3 Hamiltonian showed that the Hmodel derived from ab initio method was better than the PM3 one. The eigenvalue of the highest occupied molecular orbital plays a decisive role on the photolysis half-lives of PAHs in all descriptors studied in this work. Photolysis half-lives of three other PAHs without reported values were predicted at the end of this study.
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[1] 王连生,孔令仁, 常城,17种多环芳烃在水溶液中的光解.环境化学, 1991,10(2)∶15-20
[2] 潘相敏,陈立民,成玉等,气溶胶中多环芳烃光降解的初步研究.环境化学, 1999,18(4)∶327-332
[3] Miller J S, Olejnik D,Photolysis of Polycyclic Aromatic Hydrocarbons in Water.Wat.Res., 2001,35(1)∶233-243
[4] Smith J H, Mabey W R, Bahonos N et al.,Environmental Pathways of Selected Chemicals in Fresh Water Systems: Part II. Laboratory Studies. Interagency Energy-Environment Research Report EPA-600/7-78-074. Environmental Research Laboratory Office of Research and Development, US EPA, Athens, 1979
[5] Zepp R G, Schlotzhauer P F,Potoreactivity of Selected Aromatic Hydrocarbons in Water. In: Jones PR, Leber P. Polynuclear Aromatic Hydrocarbons. Ann Arbor Science Publishers, Ann Arbor MI, 1979,141-158
[6] Schwarzenbach R P, Gschwend P M, Imboden D M,Environmental Organic Chemistry, Second Edition. New York:John Wiley & Sons, 2003
[7] Chen J W, Peijnenburg W J G M, Quan X et al.,Is It Possibleto Develop a QSPR Model for Direct Photolysis Half-Lives of PAHs under Irradiation of Sunlight.Environ.Pollut., 2001, 114(1)∶137-143
[8] 陈景文,王帅杰,邹善伟等,不同量子化学算法在多环芳烃光解行为定量结构-性质关系(QSPR)中的应用.中国环境科学, 1999,19(2)∶102-105
[9] Chen J W,Kong L R, Zhu C M et al.,Correlation Between Photolysis Rate Constants of Polycyclic Aromatic Hydrocarbons and Frontier Molecular Orbital Energy.Chemosphere, 1996,33(6)∶1143-1150
[10] Frisch M J, Trucks G W, Schlegel H B et al., Gaussian 98, Revision A.9. Gaussian Inc.,Pittsburgh PA, 1998
[11] 葛利云,邓欢欢,吴峰等,普通小球藻引发水中苯胺光降解的研究.环境化学, 2004,23(2)∶178-182 -
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