拉曼光谱的16种多环芳烃(PAHs)特征振动光谱辨识

借助密度泛函理论中B3LYP/6-311++G(d,p)方法对美国EPA优先控制污染物中的16种多环芳烃(PAHs):萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、稠二萘、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并(a,h)蒽、二苯并[g,h,i]芘以及茚苯(1,2,3-cd)芘进行结构优化,并计算拉曼光谱振动频率和去偏振度,在此基础上辨识多环芳烃的拉曼特征光谱。研究显示,16种PAHs的拉曼振动主要分布在3个频区:200~1 000cm-1(指纹区)、1 000~1 700和3 000~3 200cm-1(基团频率区),3个频区主要振动归属分别为环变形(ring def),碳碳伸缩(CCStr)、碳氢摇摆(CHw)及其耦合振动(CCStrCCw),碳氢伸缩(CHStr)。进一步分析显示,指纹区16种PAHs的去偏振度随苯环变形振动对称性增强而降低,在该频区去偏振度最小的频移处苯环呼吸振动的对称性最强,指纹区的峰强也在此处出现最大值。任意PAHs在指纹区的最强峰之间的波数差较大,在显微拉曼光谱的可分辨范围内,因而利用指纹区的去偏振度和最强峰可将16种PAHs逐一识别。烷烃、烯烃、炔烃、醇类和酚类、脂肪醚、芳基烷基醚、醛类、酮类、羧酸、酯类、胺类、腈类、酰胺类、酸酐、芳烃的振动频率和峰强分布不完全一致,利用PAHs与这几类物质拉曼频率和峰强分布的差异可以逐一排出干扰。

水溶液的近区喇曼光谱研究

水溶物大分子周围存在着有序水分子 .这种有序水分子形成一层天然屏障 ,阻碍了大分子间的相互结合 ,也就阻碍了化学反应的快速进行 .用近区喇曼光谱研究如何打破这层壁垒 ,对人为控制化学反应意义重大 .

Tracking coherent low frequency vibrational information of Rh101 in ground and excited electronic states by broadband transient grating spectroscopy

Time-and frequency-resolved broadband transient grating(BB-TG) spectroscopy is used to distinguish between ground-and excite-electronic state vibrational coherence at different wavelengths. Qualitative theoretical analysis using double-sided Feynman diagrams indicates that a superposition of ground and excited state vibrational coherence are contained in the ground state absorption(GSA) and stimulated emission(SE) overlap band, while only the excited state is contained in the excited state absorption(ESA) band. The TG experiment, in which a white light continuum(WLC) is adopted as a probe, is conducted with rhodamine101(Rh101~+) as the target molecule. Fourier analysis of TG dynamics in a positive delay time range at specific wavelengths enables us to distinguish the low-frequency vibrational modes of Rh101 in ground-and excite-electronic states.