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

构建了用于分子束实验的真空室，并配备了线性飞行时间质谱仪来测量质量选择共振多光子电离光谱。利用该装置和另一个用于激光诱导荧光(LIF)的真空室，进行了以下研究。测量了甲基取代的含氮芳香族分子吡啶、甲基吡嗪和甲基喹啉在超音速射流中的激光激发光谱。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激光激发光谱和荧光光谱。已知这些分子在极性溶剂中有CT发射。讨论了吡啶环上的甲基取代以及与某些溶剂分子形成络合物对CT态形成的影响。5-甲基…的LiF激发光谱和烧孔光谱在超音速射流中测量了更多的DOLE单体及其与H2O、N2O、甲醇和苯的络合物。考察了5-甲基吲哚的甲基在络合物形成过程中扭转势的变化。测量了间甲腈-N_2O和间甲腈-H_2O络合物在超音速射流中的LiF激发光谱和烧孔光谱。对于每个络合物，都发现了两个异构体。发现间甲腈-N_2O和间甲腈-H_2O在一个异构体中的甲基扭转势与单体的扭转势基本相同。另一方面，另一个异构体的扭转势与单体中的扭转势有明显的不同。将这些络合物的扭转势与已测定的间甲腈-稀有气体络合物的扭转势进行了比较。测量了花菁染料NK1247的LiF激发光谱和烧孔光谱。对观测到的低频带的来源进行了研究。从分子的高效光致异构化出发，讨论了染料分子的低荧光量子产率。较少

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