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偶氮苯及其衍生物吸收光谱的密度泛函理论研究

发表时间:2018-04-13  浏览量:892  下载量:274
全部作者: 陈姝璇,孙青,吕鑫
作者单位: 厦门大学化学化工学院
摘 要: 选择一系列(含时)密度泛函理论((time-dependent) density functional theory,TD-DFT)方法和基组对偶氮苯在气相和多种溶剂环境中的结构和吸收光谱进行理论预测,并与实验结果进行比较。研究发现,TD-wB97XD/6-311+G(2d,p)//M06/6-31++G(d,p)组合方法可准确预测气相/溶剂条件下偶氮苯顺反异构体及其衍生物的结构及吸收光谱。利用此组合方法对实验中已表征的173种偶氮苯分子衍生物(取代基包括烷基、卤素、甲氧基/乙氧基、硝基、胺基等)的顺反异构体在各种环境(气相、乙醇、己烷、环己烷、氯仿、乙腈、水、苯等)中的吸收光谱进行理论预测,平均相对误差(mean relative error,MRE)为3.4 nm,平均绝对误差(mean absolute error,MAE)为15.5 nm,线性相关系数R2为0.88,并且可以较准确地预测反式-顺式吸收峰的相对位移。
关 键 词: 物理化学;含时密度泛函理论;偶氮苯;吸收光谱
Title: Extensive DFT investigation on the absorption spectra of azobenzene and its derivatives
Author: CHEN Shuxuan, SUN Qing, LÜ Xin
Organization: College of Chemistry and Chemical Engineering, Xiamen University
Abstract: The ground-state structures and absorption spectrums of cis-/trans-azobenzene in various environments (gas phase or normal organic solvents) have been explored by means of (time-dependent) density functional theory (TD-DFT) calculations with the use of nine types of density functionals and eleven types of basis sets in different sizes. The TD-wB97XD/6-311+G(2d,p)//M06/6-31++G(d,p) prediction appears to be the best in reproducing experimental data. At this very level of theory, the vertical excited energies of a total of 173 azobenzene derivatives in different environments have thus been computed and compared with the available experimental data. For the full set of absorption wavelengths concerned, the currently recommended TD-wB97XD/6-311+G(2d,p)//M06/6-31++G(d,p) prediction gives a mean relative error (MRE) of 3.4 nm and a mean absolute error (MAE) within 15.5 nm, and the linear correlation between the experimental and theoretical data gives a R2 value of 0.88. This method also correctly predicts the observed cis-trans shifts in the characteristic absorptions of those azobenzene derivatives.
Key words: physical chemistry; time-dependent density functional theory; azobenzene; absorption spectrum
发表期数: 2018年4月第7期
引用格式: 陈姝璇,孙青,吕鑫. 偶氮苯及其衍生物吸收光谱的密度泛函理论研究[J]. 中国科技论文在线精品论文,2018,11(7):660-669.
 
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