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

设计并成功地建立了反应团簇源反射式质谱仪。最初开发的红外-紫外多共振光谱与此集群源相结合，和振动光谱的反应性集群已被测量不仅在基态，而且在激发电子态。最明显的例子是酚氨团簇的光化学研究。用UV-IR-UV三色浸渍光谱法测定了苯酚-（NH_3）_3光化学反应产物的振动跃迁。在-3200 cm^-1处观察到两个尖锐的谱带，在2700-31 00 cm^-1区域观察到一个宽带。该光谱与S_（1）中的簇合物的光谱明显不同，也与NH_4+（NH_3）_2的红外光谱有很大的不同。这表明在电子激发态苯酚-（NH_3）_3中发生了氢转移。通过对苯酚-（NH_3）_4簇合物的质谱和红外吸收光谱的分析，也发现了氢转移的证据。此外，还测定了萘酚、咔唑、7-氮杂吲哚、吲哚等化合物溶剂化簇合物的红外光谱。用红外-紫外双共振光谱法测定了它们的分子量，并与从头算分子轨道计算结果进行了比较，确定了它们的分子量。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.