Study of Role of Large-Amplitute Vibrations in Dynamics of Molcular Complexes

建立了配备线性飞行时间质谱仪的分子束实验真空室，用于测量质量选择共振多光子电离谱。利用该设备和另一个用于激光诱导荧光（LIF）目的的真空室，进行了以下研究。测定了甲基取代含氮芳香分子吡啶、甲基吡嗪和甲基喹啉在超音速射流中的liff激发光谱。研究了荧光量子产率与甲基扭转运动的关系。测定了4-二甲氨基吡啶及其3-甲基和3,5 -二甲基衍生物在超音速射流中的liff激发光谱和分散荧光光谱。已知这些分子在极性溶剂中具有CT发射。讨论了吡啶环上甲基取代和与某些溶剂分子形成络合物对ct态形成的影响。测定了5-甲基林及其与H_2O、N_2O、甲醇和苯配合物在超音速射流中的liff激发和空穴燃烧光谱。研究了5-甲基吲哚在络合物形成过程中甲基扭转势的变化。测量了m-to - unitrile- n_2o和m-to - unitrile- h_2o配合物在超音速射流中的liff激发和空穴燃烧光谱。每个络合物都有两个同分异构体。在同一异构体中，间三腈- n_2o和间三腈- h_2o的甲基扭转势与单体中的甲基扭转势基本相似。另一方面，另一异构体中的扭转势与单体中的扭转势明显不同。将这些配合物的扭转电位与先前测定的间-三腈-稀有气体配合物的扭转电位进行了比较。测定了一种merocyanine染料NK1247的lif激发光谱和空穴燃烧光谱。研究了观测到的低频带的来源。从染料分子的高效光异构化角度讨论了染料分子的低荧光量子产率。少

Vacuum chamber for molecular beam experiment equipped with a linear time-of-flight mass spectrometer was constructed to measure mass-selected resonance multi-photon ionization spectra. With the equipment and another vacuum chamber for laser-induce fluorescence (LIF) purpose, following researches have been performed.1. LIF-excitation spectra of methyl-substituted nitrogen-containing aromatic molecules such as picolines, methylpyrazine and methylquinoline in supersonic jets were measured. Relation between quantum yields of fluorescence and methyl torsional motion was studied.2. LIF-excitation and dispersed fluorescence spectra of 4-dimethylaminopyridine and its 3-methyl and 3, 5-dimethyl derivatives in supersonic jets were measured. These molecules are known to have CT emission in polar solvents. Effects of methyl substitution at pyridine ring and of complex formation with some solvent molecules on CT-state formation were discussed.3. LIF-excitation and hole-burning spectra of 5-methylin … More dole monomer and its complexes with H_2O, N_2O, methanol and benzene in supersonic jets were measured. Change of the torsional potential of methyl group of 5-methylindole upon complex formation was investigated.4. LIF-excitation and hole-burning spectra of m-tolunitrile-N_2O and m-tolunitrile-H_2O complexes in supersonic jets were measured. For each complex, two isomers were found. Torsional potentials of methyl groups of m-tolunitrile-N_2O and m-tolunitrile-H_2O in one isomer were found to be almost similar with that in monomer. Out the other hand, torsional potentials in the other isomer are different appreciably from that in monomer. Torsional potentials in these complexes were compared with those in m-tolunitrile-rare gas complexes which had been determined previously.5. LIF-excitation and hole-burning spectra of a merocyanine dye, NK1247, were measured. Origin of observed low-frequency bands were investigated. Low quantum yield of fluorescence for the dye molecule was discussed in terms of high efficiency photoisomerization of the molecule. Less