Spectroscopy and Dynamics of Reactive Cluster Studied by Two-Color Laser Vibrational Spectrosopy and Quantum Chemical Calculation

研制成功了反应簇源反射质谱计。将原有的红外-紫外多共振光谱与该簇源相结合，测量了反应簇在基态和激发态下的振动光谱。最明显的例子是苯酚-氨团簇的光化学研究。采用UV-IR-UV三色浸光度法测定了苯酚-(NH_3)_3光化学反应产物的振动跃迁。观测到-3200 cm^-1区域的两个尖锐带和2700-31 00 cm^-1区域的宽带。光谱与S_(1)中的团簇有明显的不同，与NH_4+(NH_3)_2的红外光谱也有很大的不同。这表明氢转移发生在电子激发的苯酚-(NH_3)_3中。通过团簇的质谱和红外光谱分析，发现了苯酚-(NH_3)_4中氢转移的证据。此外，对萘酚、咔唑、7-氮杂素的溶剂化簇进行了红外光谱分析。用红外-紫外双共振光谱对e及其二聚体进行了测量，并通过与从头计算MO的比较确定了它们的结构。讨论了结构与光化学性质的关系。

Reflectron mass-spectrometer with reactive cluster source was designed and built succes sfully. Originally developed IR-UV multi-resonance spectroscopies were combined with this cluster source, and vibrational spectra of reactive clusters have been measured not only in the ground- state but also in the excited electronic states. The most clear example is the study on photochemistry in phenol-ammonia clusters. The vibrational transitions of the photochemical reaction products in phenol-(NH_3)_3 have been measured by UV-IR-UV three-color dip spectroscopy. Two sharp bands at -3200 cm^-1 and a broad band in the region 2700-31 00 cm^-1 are observed. The spectrum is clearly different from that of the cluster in S_(1) and also largely different from the IR spectrum of NH_4+(NH_3)_2. This suggests that hydrogen transfer occurs in electronically excited phenol-(NH_3)_3. Evidence of hydrogen trans fer hasalso been found in phenol-(NH_3)_4 based on the mass spectrum and the IR dip spectrum of the cluster. In addition, IR spectra of solvated cluster of naphthol, carbazole, 7-azaindo!e and its dimer have been measured by IR-UV double resonance spectroscopies and their slruc lure have been determind^ based on the comparison to ab initio MO calculations. The re lation between the structure and photochemical properties have been discussed.