基于密度泛函理论的C24H38O4分子外场效应研究

杜建宾; 张倩; 李奇峰; 唐延林

doi:10.7498/aps.67.20172022

摘要

各种环境毒物危害着人类的健康，塑化剂更是破坏了食品安全.为研究外电场对塑化剂主要成分之一C24H38O4（邻苯二甲酸二辛酯，dioctyl phthalate，DOP）的影响，采用密度泛函理论B3LYP方法在6-311G（d，p）基组水平上优化了不同静电场0–0.0125 a.u.（0–6.4278×109 V/m）作用下DOP分子的基态几何结构，在此基础上利用同样的方法计算了DOP分子的电偶极矩和分子总能量，最后利用含时密度泛函理论在同一基组下研究了不同外电场对DOP分子紫外-可见（UV-vis）吸收光谱产生的影响，并与实验测得的光谱图进行了比较.结果表明：分子几何构型与电场大小呈现强烈的依赖关系，分子偶极矩随着外电场的增强先减小后增加，而分子总能量随着外电场的增强先增加而后急剧减小；DOP分子激发态的振子强度随着外电场的增强而减小，UV-vis吸收峰显著红移.

关键词:

Abstract

The C24H38O4 (dioctyl phthalate, DOP) is a main component of the plasticizer. In order to study the influence of external electrical field on molecular structure and spectrum of DOP, the method B3LYP of the density functional theory at B3LYP/6-311G(d,p) level is employed to calculate geometrical parameters of the ground state of DOP molecule under different external electric fields (from 0 to 0.0125 a.u.) in this article. On this basis, the ultraviolet-visible absorption spectrum of DOP is calculated by using the time-dependent density functional theory in the same fundamental group and compared with the ultraviolet absorption peak of the molecules, measured by UNICO ultraviolet and visible spectrophotometer. Finally, by using the time-dependent density functional theory in the same fundamental group, we study wavelengths and oscillator strengths of the first twenty-six excited states of DOP molecule in external electric field. The obtained results are as follows. The strongest absorption of ultraviolet-visible absorption spectrum appears in the end absorption band from n to σ* transition. The stronger absorption occurs in the E band of benzene electronic transition from π to π*. The molecular geometry parameters are strongly dependent on the external field intensity. The dipole moment of DOP molecule is proved to first decrease and then increase with the sharp increase of external field, but the total energy first increases and then decreases with the increase of the external field intensity. The ultraviolet absorption peaks of excited states of DOP are proved to have observably red shift, and the oscillator strength sharply decreases with the increasing of the field intensity.

Keywords:

作者及机构信息

1.
廊坊师范学院物理与电子信息学院, 廊坊 065000;

2.
天津大学精密仪器与光电子工程学院, 天津 300072;

3.
贵州大学理学院物理系, 贵阳 550025

通信作者: 杜建宾, dujianbinfzf@sina.com

基金项目: 国家重点研发计划（批准号：2014YQ060773，2017YFC0803600）、河北省教育厅青年基金（批准号：QN2015219）和廊坊师范学院自然基金（批准号：LSLY201509）资助的课题.

Authors and contacts

1.
College of Physics and Electrical Information, Langfang Normal University, Langfang 065000, China;

2.
College of Precision Instrument and Optoelectronics Engineering, Tianjin University, Tianjin 300072, China;

3.
Department of Physics, Guizhou University, Guiyang 550025, China

Corresponding author: Du Jian-Bin, dujianbinfzf@sina.com

Funds: Project supported by the National Key Research and Development Program of China (Grant Nos. 2014YQ060773, 2017YFC0803600), the Young Fund of Hebei Education Department, China (Grant No. QN2015219), and the Natural Science Foundation of Langfang Normal University, China (Grant No. LSLY201509).

参考文献

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[16]	Ledingham K W D, Singhal R P, Smith D J, McCanny T, Graham P, Kilic H S, Peng W X, Wang S L, Langley A J, Taday P F, Kosmidis C 1998 J. Phys. Chem. A 102 3002
[17]	Liu X G, Cole M J, Xu Z C 2017 J. Phys. Chem. C 121 13274
[18]	Gasiorskia P, Matusiewicza M, Gondekb E, Uchaczc T, Wojtasikd K, Daneld A, Shchure Y, Kityka A V 2017 Spectrochim. Acta A 186 89
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[20]	Xu G L, Xie H X, Yuan W, Zhang X Z, Liu Y F 2012 Chin. Phys. B 21 053101
[21]	Grozema F C, Telesca R, Joukman H T, Snijders J G 2001 J. Chem. Phys. 115 10014
[22]	Wu D L, Tan B, Wan H J, Zang X Q, Xie A D 2013 Chin. Phys. B 22 123101
[23]	Kjellberg P, He Z, Pullerits T 2003 J Phys. Chem. B 107 13737
[24]	Chen X J, Luo S Z, Jiang S B, Huang W, Gao X L, Ma M Z, Zhu Z H 2004 Chin. J. Atom. Mol. Phys. 21 203 (in Chinese) [陈晓军, 罗顺忠, 蒋树斌, 黄玮, 高小玲, 马美仲, 朱正和 2004 原子与分子物理学报 21 203]
[25]	Xie A D, Xie J, Zhou L L, Wu D L, Ruan W, Luo W L 2016 Chin. J. Atom. Mol. Phys. 33 989 (in Chinese) [谢安东, 谢晶, 周玲玲, 伍冬兰, 阮文, 罗文浪 2016 原子与分子物理学报 33 989]

施引文献

[1]	Shi Z B, Yao N, Zhu Y, Zhang X M 2009 Plastic Additive 5 43 (in Chinese) [石志博, 姚宁, 朱玉, 张晓明 2009 塑料助剂 5 43]
[2]	Jin D 2010 China Chlor-Alkali 10 6 (in Chinese) [金栋 2010 中国氯碱 10 6]
[3]	Tickner J A, Schettler T, Guidotti T, McCally M, Rossi M 2001 Am. J. Ind. Med. 39 100
[4]	Li J, Si J L 2002 Chin. J. Public Health 18 241 (in Chinese) [李杰, 司纪亮 2002 中国公共卫生 18 241]
[5]	Cirillo T, Fasano E, Castaldi E, Montuori P, Cocchieri R A 2011 J. Agric. Food Chem. 59 10532
[6]	Mu X Y, Li C L, Huang Y, Shen G M, Li X X, Lei Y L, Huang L, Pang S, Li Y R, Li X F, Wang C J 2017 J. Environ. Sci.-China 37 3566 (in Chinese) [穆希岩, 李成龙, 黄瑛, 沈公铭, 李绪兴, 雷云雷, 黄岚, 逄森, 李应仁, 李学锋, 王成菊 2017 中国环境科学 37 3566]
[7]	Liu L, Shen L, Yang F, Han F, Hu P, Song M 2016 J. Appl. Spectrosc. 83 603
[8]	Li X Z, Yuan B L, Graham N 2008 ACS Symposium Series 985 364
[9]	Wu H J, Wu M, Xie M S, Liu H, Yang M, Sun F X, Du H Z 2000 Chin. J. Catal. 21 399 (in Chinese) [吴合进, 吴鸣, 谢茂松, 刘鸿, 杨民, 孙福侠, 杜鸿章 2000 催化学报 21 399]
[10]	Ellert C, Corkum P B 1999 Phys. Rev. A 59 R3170
[11]	Walsh T D G, Starch L, Chin S L 1998 J. Phys. B:At. Mol. Opt. Phys. 31 4853
[12]	Wang F H, Huang D H, Yang J S 2013 Acta Phys. Sin. 62 073102 (in Chinese) [王藩侯, 黄多辉, 杨俊升 2013 物理学报 62 073102]
[13]	Rai D, Joshi H, Kulkarni A D, Gejji S P, Pathak R K 2007 J. Phys. Chem. A 111 9111
[14]	Iwamae A, Hishikawa A, Yamanouchi K 2000 J. Phys. B:At. Mol. Opt. Phys. 33 223
[15]	Ellert C, Stapelfeldt H, Constant E 1998 Phil. Trans. R. Sol. Lond. A 356 329
[16]	Ledingham K W D, Singhal R P, Smith D J, McCanny T, Graham P, Kilic H S, Peng W X, Wang S L, Langley A J, Taday P F, Kosmidis C 1998 J. Phys. Chem. A 102 3002
[17]	Liu X G, Cole M J, Xu Z C 2017 J. Phys. Chem. C 121 13274
[18]	Gasiorskia P, Matusiewicza M, Gondekb E, Uchaczc T, Wojtasikd K, Daneld A, Shchure Y, Kityka A V 2017 Spectrochim. Acta A 186 89
[19]	Wu Y G, Li S X, Hao J X, Xu M, Sun G Y, Linghu R F 2015 Acta Phys. Sin. 64 153102 (in Chinese) [吴永刚, 李世雄, 郝进欣, 徐梅, 孙光宇, 令狐荣锋 2015 物理学报 64 153102]
[20]	Xu G L, Xie H X, Yuan W, Zhang X Z, Liu Y F 2012 Chin. Phys. B 21 053101
[21]	Grozema F C, Telesca R, Joukman H T, Snijders J G 2001 J. Chem. Phys. 115 10014
[22]	Wu D L, Tan B, Wan H J, Zang X Q, Xie A D 2013 Chin. Phys. B 22 123101
[23]	Kjellberg P, He Z, Pullerits T 2003 J Phys. Chem. B 107 13737
[24]	Chen X J, Luo S Z, Jiang S B, Huang W, Gao X L, Ma M Z, Zhu Z H 2004 Chin. J. Atom. Mol. Phys. 21 203 (in Chinese) [陈晓军, 罗顺忠, 蒋树斌, 黄玮, 高小玲, 马美仲, 朱正和 2004 原子与分子物理学报 21 203]
[25]	Xie A D, Xie J, Zhou L L, Wu D L, Ruan W, Luo W L 2016 Chin. J. Atom. Mol. Phys. 33 989 (in Chinese) [谢安东, 谢晶, 周玲玲, 伍冬兰, 阮文, 罗文浪 2016 原子与分子物理学报 33 989]

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