偶氮染料中间体及几种纺织纤维的太赫兹光谱研究
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摘要
太赫兹是频率在1012Hz的远红外电磁辐射,是国际上公认的一种新的、具有许多独特优点的辐射源,也是电磁波谱中唯一未被人熟悉的波段。太赫兹时域光谱技术正是基于太赫兹辐射的产生而发展的一项新探测技术,具有广泛的应用前景。它之所以具有广泛的应用价值,首先是因为自然界大量物质的结构振动频率位于太赫兹波段,其次是太赫兹光谱能够快速获得物质的光学特性,对研究物质在该波段的内部结构具有重要意义。我们首先将太赫兹技术应用于纺织纤维与偶氮染料中间体分子的研究,获得它们在太赫兹波段的光谱特性,同时结合量子化学对偶氮染料中间体分子进行理论计算并模拟其振动。研究表明不同的纺织纤维材料和偶氮分子中间体具有各自的特征光谱,可以用太赫兹时域光谱技术进行鉴别。
本论文的主要研究工作:
1.采用太赫兹时域光谱系统测量了两类典型的化学纤维(涤纶和芳纶)在太赫兹波段的吸收特性,通过提取其光学参数获得它们的太赫兹吸收光谱。实验表明同类纤维不同结构的化学纤维的太赫兹光谱存在明显的差异,可以用来鉴别同种纤维。由于其生产工艺的不同导致其内部结构的结晶状况与分子间作用的差异也会导致其光谱存在差异,也可以由太赫兹光谱进行鉴别。
2.测试了四种禁用偶氮染料中间体的太赫兹光谱,研究了它们在太赫兹波段的物理、化学特性。测试结果表明它们在太赫兹波段也存在吸收特征峰,可以作为指纹特征库。在此基础上,以它们的纯物质为指纹特征光谱,测量了它们两两混合物的太赫兹光谱。由混合物的太赫兹光谱可以鉴别出各纯物质的特征吸收峰,只是吸收强度有所差异,这为偶氮染料中间体的分析检验又提供了一个新的测试手段。
3.采用Gussian03软件进行了量子化学计算。利用密度泛函理论B3LYP方法在6-31G(d)基组下对2-氨基-4-硝基甲苯和对氯苯胺在0～10THz频域内进行了分子结构几何优化,并使用相同的方法和基组进行振动频率的计算。对比研究了实验和理论模拟光谱,并采用Gussian View 3.07对它们的振动频率进行了归属。
THz locates in the far-infrared electromagnetic radiation with the frequency of 1012Hz, which internationally recognized as a new the radiation source having many unique advantages. It is also the only band in the electromagnetic spectrum that is not recognized by people. Terahertz time-domain spectroscopy is a new detection technology based on the production and development of THz radiation,which has broad application prospects.The reason why it has a wide range of applications.first, because the structure vibrational frequencies of a lot of material nature is in the THz segment.secondly,The terahertz spectroscopy can quickly obtain the optical properties of the material, which has the great significance of studying the internal structure of the material in this band.We first apply the terahertz technology in the research of the textile materials and Azo dye molecules,and then obtain their spectral features in the THz segment.At the same time,we carried out theoretical calculations of the Azo dyes intermediates and simulated the molecular vibration combining with quantum chemistry.Studies have shown that the different textile fiber materials and Azo molecules have their own characteristic spectral, therefore ,terahertz time-domain spectroscopy can be used to identify.
The main reasearch work in this paper as follows:
1. Using terahertz time-domain spectroscopy system measured two typical chemical fibers (polyester and aramid) in the THz section and obtained absorption features by extracting the optical parameters of their THz absorption spectra.Experimental results show that different chemical fibers exist obvious difference in THz spectrum, so it can identify the different fiber materials; even the same type of fiber, because their different production process can lead to the difference of crystallization conditions of the internal structure and Intermolecular forces,so this will also lead to differences in spectrum.Therrfore,.different production processes of the same fibers can also be identified by the THz spectra.
2. Testing four kinds of prohibited Azo dyes intermediates THz spectroscopy to study their physical and chemical properties in the THz section. Test results show that they also have absorption characteristic peaks in the THz and can serve as a fingerprinting database in the THz band. On this basis, we measure THz spectrum of the mixture of them according to their fingerprinting characteristic spectral of pure substance.Spectrum of the mixture shows that THz spectrum of the mixture can still identify their special absorption peak in the THz spectrum of pure substance.The only difference is the absorption intensity.
3. Using Gussian03 software Carry out quantum chemical calculations. We optimizate the molecular geometry structure of the 2 - amino -4 - nitrotoluene and p-chloroaniline in the 0 ~ 10THz frequency domain with DFT B3LYP method and 6-31G(d) basis and calculate the vibrational frequencies with the same method and base group.We Comparatively study the experimental and theoretical simulated spectra and figure out the ownership of the vibration frequency using Gussian View 3.07.
本论文的主要研究工作:
1.采用太赫兹时域光谱系统测量了两类典型的化学纤维(涤纶和芳纶)在太赫兹波段的吸收特性,通过提取其光学参数获得它们的太赫兹吸收光谱。实验表明同类纤维不同结构的化学纤维的太赫兹光谱存在明显的差异,可以用来鉴别同种纤维。由于其生产工艺的不同导致其内部结构的结晶状况与分子间作用的差异也会导致其光谱存在差异,也可以由太赫兹光谱进行鉴别。
2.测试了四种禁用偶氮染料中间体的太赫兹光谱,研究了它们在太赫兹波段的物理、化学特性。测试结果表明它们在太赫兹波段也存在吸收特征峰,可以作为指纹特征库。在此基础上,以它们的纯物质为指纹特征光谱,测量了它们两两混合物的太赫兹光谱。由混合物的太赫兹光谱可以鉴别出各纯物质的特征吸收峰,只是吸收强度有所差异,这为偶氮染料中间体的分析检验又提供了一个新的测试手段。
3.采用Gussian03软件进行了量子化学计算。利用密度泛函理论B3LYP方法在6-31G(d)基组下对2-氨基-4-硝基甲苯和对氯苯胺在0～10THz频域内进行了分子结构几何优化,并使用相同的方法和基组进行振动频率的计算。对比研究了实验和理论模拟光谱,并采用Gussian View 3.07对它们的振动频率进行了归属。
THz locates in the far-infrared electromagnetic radiation with the frequency of 1012Hz, which internationally recognized as a new the radiation source having many unique advantages. It is also the only band in the electromagnetic spectrum that is not recognized by people. Terahertz time-domain spectroscopy is a new detection technology based on the production and development of THz radiation,which has broad application prospects.The reason why it has a wide range of applications.first, because the structure vibrational frequencies of a lot of material nature is in the THz segment.secondly,The terahertz spectroscopy can quickly obtain the optical properties of the material, which has the great significance of studying the internal structure of the material in this band.We first apply the terahertz technology in the research of the textile materials and Azo dye molecules,and then obtain their spectral features in the THz segment.At the same time,we carried out theoretical calculations of the Azo dyes intermediates and simulated the molecular vibration combining with quantum chemistry.Studies have shown that the different textile fiber materials and Azo molecules have their own characteristic spectral, therefore ,terahertz time-domain spectroscopy can be used to identify.
The main reasearch work in this paper as follows:
1. Using terahertz time-domain spectroscopy system measured two typical chemical fibers (polyester and aramid) in the THz section and obtained absorption features by extracting the optical parameters of their THz absorption spectra.Experimental results show that different chemical fibers exist obvious difference in THz spectrum, so it can identify the different fiber materials; even the same type of fiber, because their different production process can lead to the difference of crystallization conditions of the internal structure and Intermolecular forces,so this will also lead to differences in spectrum.Therrfore,.different production processes of the same fibers can also be identified by the THz spectra.
2. Testing four kinds of prohibited Azo dyes intermediates THz spectroscopy to study their physical and chemical properties in the THz section. Test results show that they also have absorption characteristic peaks in the THz and can serve as a fingerprinting database in the THz band. On this basis, we measure THz spectrum of the mixture of them according to their fingerprinting characteristic spectral of pure substance.Spectrum of the mixture shows that THz spectrum of the mixture can still identify their special absorption peak in the THz spectrum of pure substance.The only difference is the absorption intensity.
3. Using Gussian03 software Carry out quantum chemical calculations. We optimizate the molecular geometry structure of the 2 - amino -4 - nitrotoluene and p-chloroaniline in the 0 ~ 10THz frequency domain with DFT B3LYP method and 6-31G(d) basis and calculate the vibrational frequencies with the same method and base group.We Comparatively study the experimental and theoretical simulated spectra and figure out the ownership of the vibration frequency using Gussian View 3.07.
引文
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[2]曹俊诚.太赫兹量子级联激光器研究进展[J].物理,2006,35(8):632-636.
[3]金晓,束小建,丁武等.远红外自由电子激光太赫兹光源研究[J].物理报,2005,(5):56-57.
[4] A. Urbanowicza, A. Krotkusa, R. Adomaviciusa.et al.Terahertz emission fromfemtosecond laser excited Ge surfacesdue to the electrical field-induced optical rectification [J]. Physica B, 2007, (398): 98-101.
[5] Zhengwei Zhang, Yan Zhang, Guozhong Zhao.et al. Terahertz time-domain spectroscopy for explosive imaging [J]. OPTIK, 2007, (118): 325-329.
[6] Tong-fu Su, Xin-feng Jia, Guo-zhong Zhao.et al. Characterization of original and expanded leaf-roots of tobacco by terahertz spectroscopy and X-ray micro analysis [J]. Materials Letters, 2008, (62): 2779-2782.
[7] M.R. Kutteruf, C.M. Brown, L.K. Iwaki, et al. Terahertz spectroscopy of short-chain polypeptides [J]. Chemical Physics Letters, 2003, (375): 337-343.
[8]马晓菁,赵红卫,代斌等.次黄嘌呤及其核苷的THz光谱[J].物理学报,2008,57(6): 3429-3433.
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