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多氯联苯(PCBs)是难降解有机污染物, 2, 2, 5, 5-四氯联苯(PCB52)是PCBs的一种, 研究通过对PCB52分子加外电场的方法来降解该物质. 采用密度泛函B3LYP方法在6-311+g(d)基组水平上优化并计算了不同外电场(-0.040.04 a.u.)作用下PCB52的基态分子结构参数、分子总能量、电偶极矩和电荷分布. 然后利用含时密度泛函方法研究了PCB52分子在外电场下的前六个激发态的波长、激发能量和振子强度的影响. 结果表明: 随着外电场的增加, 1C21Cl和14C20Cl键的键长增大; PCB52的两个苯环在外加电场下, 二面角增大, 分子毒性减弱; PCB52分子能隙减小, 导致分子更容易受激发而跃迁到激发态发生还原脱氯反应. 外电场的增大, 激发态的激发能在迅速减小, 吸收波长也迅速红移, 振子强度不再为零. 表明电场作用下, 分子易于激发和解离.
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关键词:
- 2,2,5,5-四氯联苯 /
- 电场 /
- 基态 /
- 激发特性
Polychlorinated biphenyls (PCBs) are persistent organic pollutant, and 2, 2, 5, 5-tetrachlorobiphenyl is generally used as a model molecule of PCBs in some studies. PCB52 molecule is degraded under external electric fields. The molecular structure of PCB ground state is optimized by density functional theory (B3LYP) method with 6-311+g(d) basis sets. The effects of electric fields ranging from-0.04 a.u. to 0.04 a.u. are investigated on structural parameters, total energy, dipole moment and charges distribution. The transition wavelengths, oscillator strengths and excitation energies of the first six excited states under external electric fields are calculated by the time dependent density functional theory method. The result shows that the bond lengths of 1C21Cl and 14C20Cl increase with external electric field increasing. The dihedral angle of two benzene rings of PCB52 molecule increases under the electric fields, and the PCB52 molecule reduces toxicity. PCB52 molecule energy gaps decrease, leading to the fact that the molecule is susceptible to excitation to an excited state and reductive dechlorination reaction. As the increase of the applied electric field, the excitation energies rapidly decrease, absorption wavelengths are red-shifted toward longer wavelength and oscillator strength is no longer zero, which indicates that the PCB52 molecule is easily excited and dissociated.-
Keywords:
- 2,2,5,5-tetrachlorobiphenyl /
- electric field /
- ground states /
- excitation properties
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[33] Huang D H, Wang F H, Wang M J, Jiang G 2013 Acta Phys. Sin. 60 013104 (in Chinese) [黄多辉, 王藩侯, 王明杰, 蒋刚 2013 60 013104]
-
[1] Zhang Q Z, Li S Q, Qu X H, Shi X Y, Wang W X 2008 Environ. Sci. Technol. 42 7301
[2] Llansola M, Montoliu C, Boix J, Felipo V 2010 Chem. Res. Toxicol. 23 813
[3] Vasilyeva G K, Strijakova E R, Nikolaeva S N, Lebedev A T, Shea P 2010 J. Environ. Pollut. 158 770
[4] Kida T, Nakano T, Fujino Y, Matsumura C, Miyawaki K, Kato E, Akashi M 2008 Anal. Chem. 80 317
[5] Li J S, Wang X J 2010 Sichuan Environment 29 77 (in Chinese) [李俊生, 王兴戬 2010 四川环境 29 77]
[6] Yang Y, Meng G 2010 J. Appl. Phys. 107 044315
[7] Yang G Y, Zhang X C, Wang Z Y 2006 J. Molecul. Struct. Theochem 766 25
[8] Long J Y, Yi H B, Liu X K, Wang Y F 2012 Acta Chim. Sin. 70 949 (in Chinese) [龙杰义, 易海波, 刘星楷, 汪易非 2012 化学学报 70 949]
[9] Pieper D H 2005 Appl. Microbiol. Biotechnol. 67 170
[10] Liu X T, Yu G 2006 Chemsophere 63 228
[11] Semple K T, Doick K J, Wick L Y, Harms H 2007 Environ. Pollut. 150 166
[12] Du J B, Tan Y L, Long Z W 2012 Acta Phys. Sin. 61 153101 (in Chinese) [杜建宾, 唐延林, 隆正文 2012 61 153101]
[13] Xu G L, L W J, Liu Y F, Zhu Z L, Zhang X Z, Sun J F 2009 Acta Phys. Sin. 58 3058 (in Chinese) [徐国良, 吕文静, 刘玉芳, 朱遵略, 张现周, 孙金峰 2009 58 3058]
[14] Ma M Z, Zhu Z H, Chen X J, Xu G L, Zhang Y B, Mao H P, Shen X H 2005 Chin. Phys. 14 1101
[15] Xu G L, Liu X F, Xie H X, Zhang X Z, Liu Y F 2010 Chin. Phys. B 19 113101
[16] Hu Z G, Tian Y T, Li X J 2013 Chin. Phys. Lett. 30 087801
[17] Yilmaz B, Sandal S, Chen C, Carpenter D O 2006 Toxicaology 217 184
[18] Sandal S, Yilmaz B, Carpenter D O 2008 Mutat. Res. 654 88
[19] Liu P, Zhang D J, Zhan J H 2010 J. Phys. Chem. A 114 13122
[20] Cooper G, Olney T N, Brion C E 1995 Chem. Phys. 194 175
[21] Hennico G, Delhalleet 1988 J. Chem. Phys. Lett. 152 207
[22] Grozema F C, Telesca R, Joukman H T, Siebbeles L D A, Snijders J G 2001 J. Chem. Phys. 115 10014
[23] Kjeellberg P, He Z, Pullerrits T 2003 J. Phys. Chem. B 107 13737
[24] Zhu Z H, Fu Y B, Gao T, Chen Y L, Chen X 2003 J. Chin. Atom. Mol. Phys. 20 169 (in Chinese) [朱正和, 傅依备, 高涛, 陈银亮, 陈晓军 2003 原子与分子 20 169]
[25] Chaudhuri R K, Mudholkar A, Freedet K F 1997 J. Chem. Phys. 106 9252
[26] Zeng J Y 1988 Introduction to Quantum Mechanics (Beijing: Peking University Press) pp339–341 (in Chinese) [曾谨言 1988 量子力学导论(北京: 北京大学出版社) 第339–341页]
[27] Liu P 2011 Ph. D. Dissertation (Jinan: Shandong University) (in Chinese) [刘鹏 2011 博士学位论文(济南: 山东大学)]
[28] Shi Z, Yu J, Yuan Y M, Wang Z H 2000 Acta Sci. Circums. 20 (Suppl) 110 (in Chinese) [施周, 余健, 袁玉梅, 王正华 2000 环境科学学报 20(增刊)110]
[29] Lee C, Yang W T, Parr R G 1988 Phys. Rev. B 37 785
[30] Yeh M F, Hong C S 2002 J. Chem. Eng. Data 47 209
[31] Mannila E, Kolehmainen E, Rissanen K 1994 Acta Chem. Scand. 48 684
[32] Liu C Q 1990 Quantum Biology and Application (Beijing: Higher Education Press) pp12–79 (in Chinese) [刘次全 1990 量子生物学及其应用(北京: 高等教育出版社)第12–79页]
[33] Huang D H, Wang F H, Wang M J, Jiang G 2013 Acta Phys. Sin. 60 013104 (in Chinese) [黄多辉, 王藩侯, 王明杰, 蒋刚 2013 60 013104]
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