摘要
1,5-二硝基萘(DNN)是一种非常重要的化工原材料,在多个领域被广泛采用,但其分子结构和光谱的外场效应还未见报道。因此,基于密度泛函理论(DFT)中的B3LYP方法,在def2-TZVP基组水平上,对不同外电场下分子的基态几何结构进行了优化,并计算了其红外(IR)光谱。在此基础上,基于含时密度泛函理论(TDDFT)研究了外电场对DNN分子紫外-可见(UV-Vis)光谱的影响。结果表明:在0~0.02 a.u.外电场作用下,DNN分子的几何构型改变明显;诱导偶极矩与永久偶极矩的方向相同,总偶极矩随着外电场的增强而增大;分子总能量随着外电场的增强而降低;1348和1579 cm^(-1)处的红外吸收峰分别归属于N17-O18和N17-O19、N20-O21和N20-O22的对称、非对称伸缩振动,两者在外电场作用下都发生了能级劈裂,振动斯塔克效应明显;分子在200、235和353 nm附近出现3个紫外吸收峰,200和235 nm的吸收峰分别归属于E1和E2带,是由苯型体系中的π—π^(*)跃迁所产生,353 nm的吸收峰归属于B带,是由芳香族化合物中的π—π^(*)跃迁引起的;在外电场作用下,UV-Vis吸收峰出现红移,摩尔系数先增大后减小;在分子的二维UV-Vis光谱中,同步图对角线上200 nm处形成一个较强自相关峰,证明该峰对外电场变化非常敏感。总之,外电场对DNN分子的影响十分显著。这项工作为DNN的各种潜在应用提供了一定的理论指导,同时也对萘的其他硝化产物的研究有参考价值。
1,5-dinitronaphthalene(DNN)is an important chemical raw material,widely used in various fields.To study the effect of external electric field(EEF)on DNN,the B3LYP of density functional theory(DFT)is employed to optimize the ground state structure of DNN at the def2-TZVP basis set level,and its infrared(IR)spectra are obtained.Based on this,time-dependent density functional theory(TDDFT)is employed to calculate the change in UV-Vis spectra of DNN under EEF.The range of the electrostatic field is 0~0.02 a.u.in this work.The results show that the geometric configuration of DNN strongly depends on changes in EEF.The dipole moment increases with the enhancement of EEF,while the change in total energy is opposite.The IR spectra undergo energy splitting,and the vibration Stark effect is obvious.The absorption peaks of the UV-Vis spectra exhibit a red shift;the molar coefficients initially increase and then decrease.In the two-dimensional UV-Vis spectrum of DNN,there is a strong autocorrelation peak at 200 nm on the diagonal of the synchronous graph,which indicates that the peak is very sensitive to changes in EEF.In summary,EEF has a significant impact on DNN.This work provides theoretical guidance for various potential applications of DNN,and also has reference value for the study of other nitration products of naphthalene.
作者
李译铎
冯志芳
陈东明
张倩
姚宁
张平
陶亚萍
赵文来
杜建宾
LI Yi-duo;FENG Zhi-fang;CHEN Dong-ming;ZHANG Qian;YAO Ning;ZHANG Ping;TAO Ya-ping;ZHAO Wen-lai;DU Jian-bin(College of Science,Langfang Normal University,Langfang 065000,China;School of Mechanical and Electrical Engineering,North China Institute of Aerospace Engineering,Langfang 065000,China;College of Physics and Electronic Information,Luoyang Normal University,Luoyang 471934,China;Department of Computer Science and Technology,Tsinghua University,Beijing 100084,China)
出处
《光谱学与光谱分析》
北大核心
2025年第10期2760-2766,共7页
Spectroscopy and Spectral Analysis
基金
国家自然科学基金项目(NSFC22174098)资助。
关键词
1
5-二硝基萘
外电场
DFT
光谱
1,5-dinitronaphthalene
External electric field
DFT
Spectra
作者简介
李译铎,2003年生,廊坊师范学院理学院本科生,e-mail:2275329440@qq.com;通讯作者:杜建宾,E-mail:dujianbinfzf@tju.edu.cn。
