不同环境对二苯甲酮单重态和三重态结构及性质的影响

摘要
图/表
参考文献
相关文章 (2)

全文: PDF (1623 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要目的：分析二苯甲酮（BP）单重态和三重态在气相和溶剂相（环己烷、氯仿、乙醚、乙醇）中的结构和谱学性质变化。方法：采用密度泛函理论和含时密度泛函方法在CAM-B3LYP/6-311++G（d，p）基组水平下计算分析BP的几何结构、紫外吸收光谱和红外光谱，并运用极化连续介质模型考察溶剂效应。结果：BP的单重态和三重态都是非平面对称分子；单重态紫外吸收峰有2个，其中最大吸收波长λmax随溶剂极性的增大而红移；三重态吸收峰比单重态多一个，吸收强度减小。红外光谱中单重态的νC=O随着溶剂极性的增大向低波数方向移动；三重态中νC=O消失，出现一个νC-O和νC-C的混合振动峰以及C-H弯曲振动峰。结论：随着溶剂极性的增大，单重态λmax和νC=O红移，三重态紫外吸收峰均发生不同程度的红移，但三重态的几何构型及红外振动峰变化不明显。

	服务
	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	李慧丹
	徐佳禛
	牟永晓
	王朝杰

关键词 ：二苯甲酮, 密度泛函理论, 紫外吸收光谱, 红外光谱

Abstract：Objective: To study the structural and spectroscopic properties of singlet and triplet states of benzophenone in vacuum phase and solvent environments (cyclohexane, chloroform, ether, ethanol). Methods: The geometry configuration, electronic structure, ultraviolet and infrared spectroscopy of benzophenone were calculated by density functional theory (DFT) and time-dependent density functional (TD-DFT) methods with CAM-B3LYP function and 6-311++G(d, p) basis set. The solvent effects were dealt with the polarizable continuum model. Results: The singlet and triplet states of benzophenone were non-planar symmetry. The UV-vis spectra of singlet state showed two obvious absorption peaks. The maximum absorption wavelength underwent a red-shift with the increasing solvent polarity. There were three absorption peaks in triplet state and their intensities were weakened as compared with the singlet state. The C=O stretching frequency of infrared spectroscopy was shifted to the lower wave numbers in singlet state with increasing polarity while disappeared in singlet state. A new C-H bending mode and a combination of modes implying C-C and C-O stretching vibration were appeared in triplet state. Conclusion: The C=O stretching frequency and the maximum absorption wavelength are sensitive to the solvent polarity and show a red-shift with increasing solvent polarity. However, there is no striking difference between vacuum phase and solvent environments in IR absorption peaks of triplet state as well as geometry configuration.

Key words： benzophenone density functional theory ultraviolet-visible spectroscopy infrared spectroscopy

收稿日期: 2016-12-05

基金资助:国家自然科学基金资助项目（21177098）；浙江省自然科学基金资助项目（LY16B07006）。

通讯作者: 王朝杰，副教授，Email：chjwang@wmu.edu.cn

作者简介: 李慧丹（1992-），女，浙江台州人，硕士生

链接本文:

https://xb.wmu.edu.cn/CN/ 或 https://xb.wmu.edu.cn/CN/Y2017/V47/I6/406

[1] MA T, LI Z, NIU Q, et al. Double dispersant-assisted ionic liquid dispersive liquid-liquid microextraction coupled with capillary electrophoresis for the determination of benzophenone-type ultraviolet filters in sunscreen cosmetic product [J]. Electrophoresis, 2015, 36(20): 2530-2537.
[2] 朱晓丹, 路健, 韩银峰, 等. 可聚合二苯甲酮类光引发剂的合成及其光聚合性能研究[J]. 影像科学与光化学, 2013, 31(2): 140-149.
[3] 杨金梁, 张希堂, 霍新莉, 等. 含有芝麻酚-二苯甲酮结构光引发剂的合成及应用[J]. 信息记录材料, 2014, 15(4):6-13.
[4] 蒋姗, 朱晓丹, 王克敏. 新型二苯甲酮光引发剂的合成及其光聚合性能[J]. 辐射研究与辐射工艺学报, 2014, 32(4): 42-47.
[5] 张丹丹, 王璇, 王润南, 等. 2-氨基-5-氯二苯甲酮合成工艺改进[J]. 精细石油化工, 2016, 33(4): 43-46.
[6] 胡瑞省, 刘会茹, 雷克, 等. 二苯甲C=O变温红外光谱研究[J]. 石家庄学院学报, 2014, 16(6): 24-27.
[7] BEZRODNAYA T V, MEL’NIK V I, PUCHKOVSKAYA G A, et al. Vibrational and electronic spectra of benzophenone in different phase states: Ab initio, calculations and experiment[J]. J Struct Chem, 2006, 47(1): 194-199.
[8] RAPPOPOT Z, BIALI S E, KAFTOTY M. Application of the structural correlation method to ring-flip processes in benzophenones[J]. J Am Chem Soc, 1991, 22(4): 7742-7748.
[9] KHEMIRI N, MESSAOUDI S, ABDERRABBA M, et al. Photoionization of benzophenone in the gas phase: theory and experiment[J]. J Phys Chem A, 2015, 119(23): 6148-6154.
[10] SPIGHI G, GAVEAU M A, MESTDAGH J M, et al. Gas phase dynamics of triplet formation in benzophenone[J]. Phys Chem Chem Phys, 2014, 16(20): 9610-9618.
[11] TRIVEDI M K, BRANTON A, TRIVEDI D, et al. Thermal,spectroscopic and chromategramphic characterization of biofield energy treated benzophenone[J]. Sci J Anal Chem,2015, 3(6): 109-114.
[12] HOFFMANN R, SWENSON J R. Ground and excited-state geometries of benzophenone[J]. J Phys Chem, 1970, 74(2):415-420.
[13] FLEISCHER E B, SUNG N, HAWKINSON S. Crystal structure of benzophenone[J]. J Phys Chem, 1968, 72(12): 4311-4312.
[14] SETT P, MISRA T, CHATTOPADHYAY S, et al. DFT calculation and Raman excitation profile studies of benzophenone molecule[J]. Vib Spectrosc, 2007, 44(2): 331-342.
[15] RAVI KUMAR V, VERMA C, UMAPATHY S. Molecular dynamics and simulations study on the vibrational and electronic solvatechromism of benzophenone[J]. J Chem Phys, 2016, 144(6): 064302.
[16] 汪勇, 王惠钢. 二苯甲酮(BP)S4态的动态结构[J]. 浙江理工大学学报, 2013, 30(4): 604-608.