拉曼技术2精讲.ppt

Some Raman Advantages Watch for Fluorescence Selection Rule for Raman Scattering Must be change in polarizability Non-Polar groups such as C-S, S-S, C=C, C?C (triple bond), N=N and heavy atoms (I, Br, Hg) strong scatterers Symmetric stretching vibrations are much stronger scatterers than asymmetric stretching vibrations Polarization Effects Polarization of CCl4 Polarization of CHCl3 Raman位移 拉曼光谱与有机结构 Vibrational modes of methane (CCl4) Infrared and Raman Spectrum of CCl4 Raman Spectroscopy Relatively simple and non-destructive structure analysis technique of carbon materials Powerful tool for the structural characterization of diamond or amorphous carbon materials. NSOM Raman Imaging Chemical Mapping Chemical Imaging * Here are some reasons why someone would prefer to use Raman Spectroscopy. ? Non-destructive to samples (minimal sample prep) ? Higher temperature studies possible (don’t care about IR radiation) ? Easily examine low wavenumber region: 100 cm-1 readily achieved. ? Better microscopy; using visible light so can focus more tightly. ? Easy sample prep: water is an excellent solvent for Raman. Can probe sample through transparent containers (glass or plastic bag). Spectrum of anthracene. A: using Ar+ laser at 514.5 nm. B: using Nd:YAG laser at 1064 nm. Want to use short wavelength because scattering depends on 4th power of frequency. …BUT… Want to use long wavelength to minimize chance of inducing fluorescence. 对称中心分子CO2，CS2等，选律不相容。 无对称中心分子（例如SO2等），三种振动既是红外活性振动，又是拉曼活性振动。 选律 ?1 ?2 ?3 ?4 拉曼活性 红外活性 红外活性 振动自由度：3N- 4 = 4 拉曼光谱—源于极化率变化 红外光谱—源于偶极矩变化 对不同物质： ??不同； 对同一物质： ??与入射光频率无关；表征分子振-转能级的特征物理量；定性与结构分析的依据； Raman散射的产生：光电场E中，分子产生诱导偶极距? ? = ?E ? 分子极化率； 由拉曼光谱可以获得有机化合物的各种结构信息： 2）红外光谱中，由C ?N，C=S，S-H伸缩振动产生的谱带一般较弱或强度可变，而在拉曼光谱中则是强谱带。 3）环状化合物的对称呼吸振动常常是最强的拉曼谱带。 1）同种分子的非极性键S-S，C=C，N=N，C?C产生强拉曼谱带， 随单键?双键?三键谱带强度增加。 4）在拉曼光谱中，X=Y=Z，C=N=C，O=C=O-这类键的对称伸缩振动是强谱带，反这类键的对称伸缩振动是弱谱带。红外光谱与此相反。 5）C-C伸缩振动在拉曼光谱中是强谱带。 6）醇和烷烃的拉曼光谱是相似的：I. C